Processes to produce poly alpha-olefin trimers

ABSTRACT

The present disclosure generally relates to processes to produce alpha-olefin oligomers and poly alpha-olefins. In an embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions to form a first reactor effluent. The alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene. The method includes introducing the first reactor effluent, a second alpha-olefin and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. Ser. No. 16/270,085, filed Feb.7, 2019, which claims priority to and benefit of U.S. Ser. No.62/629,200, filed Feb. 12, 2018, and U.S. Ser. No. 62/732,311, filedSep. 17, 2018.

This application is related to the U.S. patent application Ser. No.16/537,364, (2019EM302) entitled “Metallocene Dimer Selective Catalystsand Processes to Produce Poly Alpha-Olefin Dimers,” and U.S. patentapplication Ser. No. 62/16/537,381, (2019EM304) entitled “Processes toProduce Poly Alpha-Olefin Trimers and Apparatus Therefor;” having commoninventors and assignee and filed on the same date herewith, thedisclosures of which are incorporated by reference herein in theirentireties.

FIELD

The present disclosure generally relates to processes to producealpha-olefin oligomers and poly alpha-olefins.

BACKGROUND

As society looks to curb carbon emission, equipment builders haveaccelerated design changes to improve energy efficiency. For example,passenger vehicles have drastically modified the design of theirinternal combustion engines, trending toward smaller engines thatoperate at higher (and more efficient) temperatures. There has also beena significant rise in the design of electrified vehicles, and in somedesigns, equipment builders have eliminated the internal combustionengine in favor of electric vehicles. Similar trends can be observed inindustrial equipment design.

Alpha-olefins and poly alpha-olefins (PAOs), such asvinylidene-terminated PAOs, are used as intermediates in the manufactureof many commercial products such as lubricant base oil components,basestocks, and surfactants.

As a result of the equipment changes mentioned above, lubricantrequirements have generally become more stringent. For example, therehave been multiple engine oil viscosity grades added to development overthe past decade (e.g. 0W-8, 0W-12, 0W-16). These engine oils requireextremely low viscosity base oils without significantly increasingvolatility of the lubricant. These lubricants are also required todeliver outstanding oxidative stability. Additionally electric vehicleshave brought new and diverse challenges for driveline fluids and coolingsystems, which require tailored lubricant design.

While mineral-oil base stocks are widely available, they generally lacktailored performance to meet specific lubricant needs. When analyzingavailable Group III base stocks, for example, nearly all suppliers offerthree or four grades ranging from 3 cSt to 8 cSt. For very low viscosityengine oils (e.g. 0W-8), for example, these base stocks are ofteninsufficient to meet both volatility and viscometric targets.

While polyalphaolefins (PAOs) have a wide availability of viscositygrades, the vast majority of commercial low viscosity PAOs (below 10 cStKV100) are produced from BF₃ catalysts, which are difficult to tailor tospecific product performance.

Catalyst systems to selectively produce solely or predominantlyalpha-olefin dimers (e.g., >80%) at high yields and with high vinylideneunsaturation would allow for better tailoring of PAO molecules (throughtwo-step processing or further functionalization), but such catalystsystems remain elusive. For example, conventional metallocene catalystsystems, such as supported dimethylsilyl bis(2-methyl-4-phenyl-indenyl)zirconium dimethyl, typically produce about 50% vinyl and about 50%vinylidene terminal unsaturations (of the termini that are unsaturated).Conventional metallocene catalyst systems to construct high vinylidenedimerized olefins require the use of an alumoxane, aluminum alkyl, orionic activator, and in some cases the presence of hydrogen. Certainconventional processes to produce alpha-olefin dimers utilize bridgedmetallocenes, such as bis(cyclopentadienyl)zirconium dichloride, in thepresence of methyl alumoxane (MAO), trialkylaluminum, or higher alkylalumoxane and an activator such as trimethyl aluminum. Such processescan produce predominantly vinylidene dimer olefins at high yields, butlack in catalyst efficiency, kinetics, and/or high product yield.

An exemplary PAO molecule is a “hybrid trimer” which is a reactionproduct of a metallocene dimer, such as a PAO dimer, with linearalpha-olefin (LAO) using an acid catalyst system, e.g., BF₃-alcoholpromoter catalyst system. For example, a hybrid C₃₀ trimer is a reactionproduct of a C₂₀ metallocene PAO dimer and C₁₀ LAO. Conventional methodsof forming hybrid trimers involve reaction of a PAO dimer feedstock thatcontains a significant amount of disubstituted vinylene. Thedisubstituted vinylene, however, is not highly reactive when added to aBF₃ catalyzed conventional reactor, and the reaction kinetics are veryslow. In addition, the unreacted dimer in the stream going into the BF₃catalyzed conventional reactor contaminates the stream produced from theBF₃ process and reduces the value of that reactor effluent.

Furthermore, conventional plants for the production of PAO molecules,such as hybrid trimers, can generate a PAO dimer from a firstoligomerization reactor. The PAO dimer product from the firstoligomerization reactor is of such poor quality (e.g., there are timers,tetramers, and higher oligomers) that it is enriched via a separationstage prior to being fed into a second oligomerization reactor. Thisprocess involves a separation stage, e.g., a distillation operation,prior to a second oligomerization reactor because feeding the trimer andhigher (tetramer+) oligomers to the second oligomerization reactorproduces an undesired heavier product from the second oligomerizationreaction. The additional equipment, operators, and downtime involved forthe separation stage, for example, can be a burden in terms of cost andefficiencies.

Therefore, there is a need for processes to selectively produce PAOdimers, with high vinylidene and very low vinylene content, at highcatalyst efficiency, good kinetics, and high conversion. There is also aneed for improved processes and apparatus for producing PAOs, such aslow viscosity PAOs including hybrid trimers, from feedstocks containingthe PAO dimers.

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SUMMARY

The present disclosure generally relates to processes to producealpha-olefin oligomers and poly alpha-olefins.

In at least one embodiment, a process to produce a poly alpha-olefin(PAO) includes introducing a first alpha-olefin and a first catalystsystem comprising a metallocene compound into a continuous stirred tankreactor or a continuous tubular reactor under first reactor conditionsto form a first reactor effluent. The alpha-olefin is introduced to thereactor at a flow rate of about 100 g/hr. The first reactor effluentincludes PAO dimer comprising at least 96 mol % of vinylidene and 4 mol% or less of trisubstituted vinylene and disubstituted vinylene, basedon total moles of vinylidene, trisubstituted vinylene, and disubstitutedvinylene. The method includes introducing the first reactor effluent, asecond alpha-olefin and a second catalyst composition comprising an acidcatalyst into a second reactor under second reactor conditions to form asecond reactor effluent comprising PAO trimer.

In at least one embodiment, a blend includes a PAO product of thepresent disclosure.

Further areas of applicability will become apparent from the descriptionprovided herein. The description and specific examples in this summaryare intended for purposes of illustration only and are not intended tolimit the scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above-recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments.

FIG. 1 shows a conventional apparatus for alpha-olefin processing.

FIG. 2 is an example apparatus for forming poly alpha-olefins accordingto at least one embodiment.

FIG. 3 is a plot of oligomer distribution at various temperaturesaccording to at least one embodiment.

FIG. 4 is a plot of oligomer distribution at various temperaturesaccording to at least one embodiment.

FIG. 5 is a bar graph comparing mole percent vinylidene according to thepolymerization temperature of catalysts according to at least oneembodiment.

FIG. 6 is a graph comparing mole percent vinylidene versus M_(n) of1-decene oligomers produced using catalysts and methods according to atleast one embodiment.

FIG. 7 is a graph illustrating traction coefficient versus slide torolling ratio (%), according to at least one embodiment.

FIG. 8 is a graph illustrating traction coefficient versus slide torolling ratio (%), according to at least one embodiment.

FIG. 9 is a graph illustrating traction coefficient versus slide torolling ratio (%), according to at least one embodiment.

FIG. 10 is a graph illustrating traction coefficient versus slide torolling ratio (%), according to at least one embodiment.

FIG. 11 is a graph illustrating traction coefficient versus slide torolling ratio (%), according to at least one embodiment.

FIG. 12 is a graph illustrating traction coefficient versus slide torolling ratio (%), according to at least one embodiment.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. It is contemplated that elements and features of oneexample may be beneficially incorporated in other examples withoutfurther recitation.

DETAILED DESCRIPTION

The present disclosure provides processes for producing polyalpha-olefins using metallocene catalyst compounds having asymmetricunbridged metallocenes. In some examples, these metallocenes containindacenyl-type ligands. Catalyst systems comprising such compounds canbe used. The catalyst systems and processes incorporating such catalystsystems rival and/or surpass conventional catalyst systems in producingalpha-olefin oligomers and polymers.

Relative to conventional catalysts and catalyst systems, the catalystsand catalyst systems described herein can selectively producealpha-olefin dimers at high product yield (high linear alpha-olefinconversion) and with very high vinylidene unsaturation with very highcatalyst efficiency (low catalyst loading), high conversion, and goodkinetics. In at least one example, the inventors have found that thecatalyst systems disclosed herein can produce dimer selective olefins(greater than 90%), with >95 wt % vinylidene and 0 wt % vinylenecontent.

The present disclosure also provides processes and apparatus forproducing alpha-olefin oligomers from feedstocks containingpredominantly PAO dimers. In an example, the inventors have found that aso-called “hybrid trimer”, which can be formed from a reaction of a PAOdimer with an alpha-olefin monomer, can be produced in high yields. Theinventors have found that a higher purity PAO dimer feedstock, havinglow amounts of trimer, tetramer, and higher oligomers, can form higheramounts of the hybrid trimer relative to conventional processes. Inaddition, the inventors have found that reducing (or eliminating) theamount of disubstituted vinylene in the PAO dimer feedstock produces aPAO hybrid trimer at higher yields and higher purity relative toconventional processes.

The present disclosure also provides processes and apparatus forproducing alpha-olefin oligomers. In an example, the process eliminatesthe need for a separation stage between a first oligomerizationoperation and a second oligomerization operation. The inventors havefound that PAO trimer produced from a process, which includes a firstand second oligomerization, meets and/or exceeds conventional processyields of PAO trimer, even while removing the separation operationbetween the two oligomerizations. This can reduce cost and increase theefficiencies of production relative to conventional processes andapparatus.

Processes and apparatus of the present disclosure can provide one ormore the following:

-   -   a. No alumina specie present in the PAO product (able to not        have to remove Al as it can be considered an impurity for final        product; preferable to not have to reduce LAO isomerization        which leads to yield loss)        -   i. >60% dimer selectivity at a catalyst productivity            of >10,000 g PAO/g cat without the use of alumoxane        -   ii. >60% dimer selectivity at a catalyst productivity            of >10,000 g PAO/g cat without the use of alumoxane nor            alkyl alumina        -   iii. >60% dimer selectivity at a catalyst productivity            of >10,000 g PAO/g cat with <500 ppm of an alkyl alumina        -   iv. >60% dimer selectivity at a catalyst productivity            of >10,000 g PAO/g cat with <20 ppm of an alkyl alumina        -   v. >60% dimer selectivity at a catalyst productivity            of >10,000 g PAO/g cat with <2% LAO isomerization    -   b. Activity with selectivity (e.g., more efficient production of        high dimer)        -   i. >60% dimer selectivity with catalyst productivity >10,000            g PAO/g cat        -   ii. >60% dimer selectivity with catalyst activity >2,000 g            PAO/mol cat sec        -   iii. >90% dimer selectivity with catalyst            productivity >60,000 g PAO/g cat    -   c. Low residence times (which is another indicator of higher        efficiency)        -   i. <24 hours; preferably <10 hours; preferably <5 hours    -   d. Vinylidene purity (useful for functionalization by        alkylation, further oligomerization)        -   i. >90%; preferably >95%    -   e. Catalyst family        -   i. New type of catalyst specifically suitable for highly            efficient production of high vinylidene dimers.

Processes and apparatus of the present disclosure can provide one ormore the following:

-   -   continuous processes,    -   PAO products having an M_(n) below 300,    -   Processes at activity above 2,000 gPAO/s·mol with low M_(n),    -   Processes at conversion above 80% with low M_(n),    -   Processes at conversion above 80% with high vinylidene,    -   Processes can operate at higher temperature of, for example,        120-148.5° C.,    -   Processes with reduced LAO isomerization without alkyl alumina,    -   Processes can use C₆-C₂₀ LAOs,    -   Processes can optionally be MAO-free,    -   Processes can be optionally alkyl-alumina free.

For the purposes of this present disclosure, and unless otherwisespecified, the term “alkyl” or “alkyl group” interchangeably refers to asaturated hydrocarbyl group consisting of carbon and hydrogen atoms. Analkyl group can be substituted or unsubstituted and can be linear,branched, or cyclic.

For the purposes of this present disclosure, and unless otherwisespecified, the term “cycloalkyl” or “cycloalkyl group” interchangeablyrefers to a saturated hydrocarbyl group wherein the carbon atoms formone or more ring structures.

For the purposes of this present disclosure, and unless otherwisespecified, the term “alkenyl” or “alkenyl group” interchangeably refersto a linear unsaturated hydrocarbyl group comprising a C═C bond therein.

For the purposes of this present disclosure, and unless otherwisespecified, the term “cycloalkenyl” or “cycloalkenyl group”interchangeably refers to cyclic hydrocarbyl group comprising a C═C bondin the ring.

For the purposes of this present disclosure, and unless otherwisespecified, the term “aryl” or “aryl group” interchangeably refers to ahydrocarbyl group comprising an aromatic ring structure therein.

The term “branched (such as branched linear)” is defined to mean abranched group that is not dendritic (i.e., branch on branch) orcrosslinked, typically a branched (such as branched linear) group is alinear group that has one or more branches.

For the purposes of this present disclosure, and unless otherwisespecified, a substituted group refers to a group in which at least oneatom is replaced by a different atom or a group. Thus, a substitutedalkyl group is an alkyl group in which at least one hydrogen atom isreplaced by a hydrocarbyl group, a halogen, any other non-hydrogengroup, and/or at least one carbon atom and hydrogen atoms bonded theretois replaced by a different group. As a non-limiting example, asubstituted group is a radical in which at least one hydrogen atom hasbeen substituted with a heteroatom or heteroatom containing group, suchas with at least one functional group, such as halogen (Cl, Br, I, F),NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃,SnR*₃, PbR*₃, and the like or where at least one heteroatom has beeninserted within the hydrocarbyl radical, such as halogen (Cl, Br, I, F),O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂, PbR*₂, andthe like, where R* is, independently, hydrogen or a hydrocarbyl.

For the purposes of this present disclosure, and unless otherwisespecified, the terms “hydrocarbyl radical,” “hydrocarbyl group,” or“hydrocarbyl” interchangeably refer to a group consisting of hydrogenand carbon atoms only. A hydrocarbyl group can be saturated orunsaturated, linear or branched, cyclic or acyclic, aromatic, ornon-aromatic.

For the purposes of this present disclosure, and unless otherwisespecified, substituted hydrocarbyl radicals are radicals in which atleast one hydrogen atom has been substituted with a heteroatom orheteroatom containing group, such as with at least one functional group,such as halogen (Cl, Br, I, F), NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where atleast one heteroatom has been inserted within the hydrocarbyl radical,such as halogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*,SiR*₂, GeR*₂, SnR*₂, PbR*₂, and the like, where R* is, independently,hydrogen or a hydrocarbyl.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this present disclosure, when aradical is listed, it indicates that radical type and all other radicalsformed when that radical type is subjected to the substitutions definedabove. Alkyl, alkenyl, and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

For the purposes of this present disclosure, and unless otherwisespecified, silylcarbyl radicals (also referred to as silylcarbyls,silylcarbyl groups or silylcarbyl substituents) are radicals in whichone or more hydrocarbyl hydrogen atoms have been substituted with atleast one SiR*₃ containing group or where at least one —Si(R*)₂— hasbeen inserted within the hydrocarbyl radical where R* is independently ahydrocarbyl or halocarbyl radical, and two or more R* may join togetherto form a substituted or unsubstituted saturated, partially unsaturatedor aromatic cyclic or polycyclic ring structure. Silylcarbyl radicalscan be bonded via a silicon atom or a carbon atom.

For the purposes of this present disclosure, and unless otherwisespecified, substituted silylcarbyl radicals are silylcarbyl radicals inwhich at least one hydrogen atom has been substituted with at least onefunctional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, GeR*3, SnR*₃, PbR₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the silylcarbylradical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

For the purposes of this present disclosure, and unless otherwisespecified, halocarbyl radicals are radicals in which one or morehydrocarbyl hydrogen atoms have been substituted with at least onehalogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF₃).

For the purposes of this present disclosure, and unless otherwisespecified, substituted halocarbyl radicals are radicals in which atleast one halocarbyl hydrogen or halogen atom has been substituted withat least one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂,AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*3, SnR*₃, PbR*₃, and the like orwhere at least one non-carbon atom or group has been inserted within thehalocarbyl radical such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—,═P—, —As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—,—Sn(R*)₂—, —Pb(R*)₂— and the like, where R* is independently ahydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical. Additionally, two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

For the purposes of this present disclosure, and unless otherwisespecified, germanyl radicals (also referred to as germanyls, germanylgroups or germanyl substituents) are radicals in which one or morehydrocarbyl hydrogen atoms have been substituted with at least one GeR*3containing group or where at least one —Ge(R*)₂— has been insertedwithin the hydrocarbyl radical where R* is independently a hydrocarbylor halocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure. Germanyl radicals can bebonded via a silicon atom or a carbon atom.

For the purposes of this present disclosure, and unless otherwisespecified, substituted germanyl radicals are germanyl radicals in whichat least one hydrogen atom has been substituted with at least onefunctional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, SnR*₃, PbR₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the germanylradical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

For the purposes of this present disclosure, and unless otherwisespecified, the term “Cn” group or compound refers to a group or acompound comprising carbon atoms at total number thereof of n. Thus, a“Cm-Cn” group or compound refers to a group or compound comprisingcarbon atoms at a total number thereof in the range from m to n. Thus, aC₁-C₅₀ alkyl group refers to an alkyl group comprising carbon atoms at atotal number thereof in the range from 1 to 50.

For the purposes of this present disclosure, and unless otherwisespecified, the term “olefin,” alternatively termed “alkene,” refers toan unsaturated hydrocarbon compound having a hydrocarbon chaincontaining at least one carbon-to-carbon double bond in the structurethereof, wherein the carbon-to-carbon double bond does not constitute apart of an aromatic ring. The olefin may be linear, branched, or cyclic.For purposes of this specification and the claims appended thereto, whena polymer or copolymer is referred to as comprising an olefin,including, but not limited to ethylene, propylene, and butene, theolefin present in such polymer or copolymer is the polymerized form ofthe olefin. For example, when a copolymer is said to have an “ethylene”content of 35 wt % to 55 wt %, it is understood that the mer unit in thecopolymer is derived from ethylene in the polymerization reaction andsaid derived units are present at 35 wt % to 55 wt %, based upon theweight of the copolymer. A “polymer” has two or more of the same ordifferent mer units. A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. “Different” as usedto refer to mer units indicates that the mer units differ from eachother by at least one atom or are different isomerically. Thus, an“olefin” is intended to embrace all structural isomeric forms ofolefins, unless it is specified to mean a single isomer or the contextclearly indicates otherwise. An oligomer is a polymer having a lowmolecular weight, such as an Mn of 21,000 g/mol or less (such as 10,000g/mol or less), and/or a low number of mer units, such as 100 mer unitsor less (such as 75 mer units or less).

For the purposes of this present disclosure, and unless otherwisespecified, the term “alpha-olefin” refers to an olefin having a terminalcarbon-to-carbon double bond in the structure thereof ((R′R″)—C═CH₂,where R′ and R″ is independently hydrogen or any hydrocarbyl group; suchas R′ is hydrogen and R″ is an alkyl group). A “linear alpha-olefin” isan alpha-olefin defined in this paragraph wherein R′ is hydrogen, and R″is hydrogen or a linear alkyl group. Non-limiting examples of α-olefinsinclude ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene,1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene,1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene,5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, andvinylnorbornane. Non-limiting examples of cyclic olefins and diolefinsinclude cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The term “vinyl” refers to an olefin having the following formula:

wherein R is a hydrocarbyl group, such as a saturated hydrocarbyl group,such as an alkyl group.

The term “vinylidene” refers to an olefin having the following formula:

wherein R^(m) and R^(n) are each independently a hydrocarbyl group, suchas a saturated hydrocarbyl group, such as alkyl group. Vinylidenes are1,1-disubstituted vinylene groups.

The term “disubstituted vinylene” refers to:

-   -   (i) an olefin having the following formula:

or

-   -   (ii) an olefin having the following formula:

or

-   -   (iii) a mixture of (i) and (ii) at any proportion thereof,        wherein R^(m) and R^(n), the same or different at each        occurrence, are each independently a hydrocarbyl group, such as        saturated hydrocarbyl group such as alkyl group. Disubstituted        vinylenes represent only 1,2-disubstituted vinylene groups and        do not include vinylidenes, or 1,1-disubstituted vinylenes. The        term “vinylene,” as used herein, is an alternative term for        “disubstituted vinylene” only and not as a generic class of        multiple vinylene species.

The term “trisubstituted vinylene” means an olefin having the followingformula:

wherein R^(m), R^(n), and R^(p) are each independently a hydrocarbylgroup, such as a saturated hydrocarbyl group, such as alkyl group, oralternatively R^(m) and R^(n) can together form a non-aryl ringstructure with R^(p) being a pendant hydrocarbyl group.

For the purposes of this present disclosure, and unless otherwisespecified, “poly alpha-olefin(s)” (PAO(s)) are polymers of one or morealpha-olefin monomers, such as an oligomer of one or more alpha-olefins.PAOs are polymeric, typically oligomeric, molecules produced from thepolymerization/oligomerization reactions of alpha-olefin monomermolecules in the presence of a catalyst system. Thus, the PAO can be adimer (resulting from two terminal olefin molecules), a trimer(resulting from three terminal olefin molecules), a tetramer (resultingfrom four terminal olefin molecules), or any other oligomer or polymercomprising two or more structure units derived from one or more terminalolefin monomer(s). The PAOs formed in the present disclosure have akinematic viscosity (at 100° C.) of 3,000 cSt or less as determined byASTM D445, or have an M_(n) of 20,000 g/mol or less as determined by GC(as described herein), or have a combination thereof.

The PAO molecule can be highly regio-regular, such that the bulkmaterial may exhibit an isotacticity, or a syndiotacticity when measuredby ¹³C NMR. The PAO molecule can be highly regio-irregular, such thatthe bulk material can be substantially atactic when measured by ¹³C NMR.A PAO material made by using a metallocene-based catalyst system istypically called a metallocene-PAO, and a PAO material made by usingtraditional non-metallocene-based catalysts (e.g., Lewis acids,supported chromium oxide, and the like) is typically called aconventional PAO.

For the purposes of this present disclosure, and unless otherwisespecified, the term “carbon backbone” refers to the longest straightcarbon chain in the molecule of the compound or the group in question.“Branches” or “pendant groups” interchangeably refer to any non-hydrogengroup connected to the carbon backbone other than those attached to thecarbon atoms at the very ends of the carbon backbone. As used herein,the term “length” of a pendant group is defined as the total number ofcarbon atoms in the longest carbon chain in the pendant group, countingfrom the first carbon atom attached to the carbon backbone and endingwith the final carbon atom therein, without taking into considerationany substituents or pendant groups on the chain. In some embodiments,the pendant group is free of substituents comprising more than 2 carbonatoms (or more than 1 carbon atom), or is free of any substituent. Apendant group may contain a cyclic group or a portion thereof in thelongest carbon chain, in which case half of the carbon atoms in thecyclic group are counted toward the length of the pendant group. Thus,by way of examples, a linear Ca pendant group has a length of 8; each ofthe pendant groups PG-1 (cyclohexylmethylene) and PG-2 (phenylmethylene)has a length of 4; and each of the pendant groups PG-3(o-heptyl-phenylmethylene) and PG-4 (p-heptylphenylmethylene) has alength of 11. Where a PAO molecule contains multiple pendant groups, thearithmetic average of the lengths of all such pendant groups iscalculated as the average length of all pendant groups in the PAOmolecule.

In the present disclosure, any metallocene compound may have one or moreoptical isomers. All metallocene compounds identified herein by name orstructure shall include all possible optical isomers thereof andmixtures of any such optical isomers. For example, metallocene compoundMe₂Si(Me₄Cp)(3-PrInd)ZrMe₂ shall include the following two opticalisomers and mixtures thereof, even if only one structure is given whenit is described:

For the purposes of this present disclosure, and unless otherwisespecified, the term “substantially all” with respect to PAO moleculesmeans at least 90 mol % (such as at least 95 mol %, at least 98 mol %,at least 99 mol %, or even 100 mol %).

For the purposes of this present disclosure, and unless otherwisespecified, the term “substantially free of” with respect to a particularcomponent means the concentration of that component in the relevantcomposition is no greater than 10 mol % (such as no greater than 5 mol%, no greater than 3 mol %, no greater than 1 mol %, or about 0%, withinthe bounds of the relevant measurement framework), based on the totalquantity of components of the relevant composition.

For the purposes of this present disclosure, and unless otherwisespecified, a “reactor” refers to one or more vessels configured toperform oligomerization processes.

For the purposes of this present disclosure, and unless otherwisespecified, a “metallocene” catalyst compound is a transition metalcatalyst compound having one, two or three, typically one or two,substituted or unsubstituted cyclopentadienyl ligands bound to thetransition metal, typically a metallocene catalyst is an organometalliccompound containing at least one π-bound cyclopentadienyl moiety (orsubstituted cyclopentadienyl moiety). Substituted or unsubstitutedcyclopentadienyl ligands include substituted or unsubstituted indenyl,fluroenyl, indacenyl, benzindenyl, and the like.

For the purposes of this present disclosure, and unless otherwisespecified, the terms “catalyst” and “catalyst compound” are defined tomean a compound capable of initiating catalysis and/or of facilitating achemical reaction with little or no poisoning/consumption. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor.

A “catalyst system” is a combination of at least one catalyst compound,at least one activator, and optional co-activator, where the system canpolymerize/oligomerize monomers to form polymer/oligomer.

For the purposes of this present disclosure, and unless otherwisespecified, a scavenger is a compound typically added to facilitateoligomerization/polymerization by scavenging impurities. Some scavengersmay also act as activators and may be referred to as co-activators. Aco-activator, that is not a scavenger, may be used in conjunction withan activator in order to form an active catalyst. In some embodiments, aco-activator can be pre-mixed with the catalyst compound to form analkylated catalyst compound.

For the purposes of this present disclosure, and unless otherwisespecified, all kinematic viscosity values in the present disclosure areas determined according to ASTM D445. Kinematic viscosity at 100° C. isreported herein as KV100, and kinematic viscosity at 40° C. is reportedherein as KV40. Unit of all KV100 and KV40 values herein is cSt, unlessotherwise specified.

For the purposes of this present disclosure, and unless otherwisespecified, all viscosity index (VI) values in the present disclosure areas determined according to ASTM D2270.

For the purposes of this present disclosure, and unless otherwisespecified, all Noack volatility (NV) values in the present disclosureare as determined according to ASTM D5800 and units of all NV values arewt %.

For the purposes of this present disclosure, and unless otherwisespecified, bromine number values in the present disclosure aredetermined according to ASTM D 1159.

For the purposes of this present disclosure, and unless otherwisespecified, rotating pressure vessel oxidation test (RPVOT) values in thepresent disclosure are determined according to ASTM D2272.

For the purposes of this present disclosure, and unless otherwisespecified, all numerical values within the detailed description and theclaims herein are modified by “about” or “approximately” the indicatedvalue, and consider experimental error and variations that would beexpected by a person having ordinary skill in the art.

For the purposes of this present disclosure, and unless otherwisespecified, all percentages of pendant groups, terminal carbon chains,and side chain groups are by mole, unless specified otherwise. Percentby mole is expressed as “mol %,” and percent by weight is expressed as“wt %.”

For the purposes of this present disclosure, and unless otherwisespecified, all molecular weight data are in the unit of g·mol⁻.

The following abbreviations may be used through this specification: Cpis cyclopentadiene or cyclopentadienyl; Me is methyl, Ph is phenyl, Etis ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu isbutyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiarybutyl, nBu is normal butyl, TMS is trimethylsilyl, TIBAL istriisobutylaluminum, TNOAL or TNOA is trin-octylaluminum, MAO ismethylalumoxane, pMe is para-methyl, Ar* is 2,6-diisopropylaryl, Bz orBn are interchangeably benzyl, THF is tetrahydrofuran, RT is roomtemperature (i.e., approximately 23° C.), and tol is toluene.

I. Metallocene Dimer Selective Process

The present disclosure includes catalyst compounds that can dimerizealpha-olefins, e.g., linear alpha-olefins, in the presence ofmetallocene catalysts to produce PAO dimers with high selectivity andhigh yields, with very low amounts of trimers, tetramers, and higheroligomers (if any), where the higher oligomers are oligomers that havedegree of polymerization of 5 or more. As used herein, “degree ofpolymerization” refers to the number of monomeric units of an oligomer.For example, an oligomer having a degree of polymerization of 3 is anoligomer that is the reaction product of 3 monomers. A “dimer” has adegree of polymerization of 2, and a “trimer” has a degree ofpolymerization of 3.

In addition, the catalyst compounds can produce, based on the amount ofPAO dimers produced, very low disubstituted and trisubstituted vinylenecontent (e.g., about 0 mol %), very low trisubstituted unsaturation(e.g., about 5 mol % or lower), and very high vinylidene content (e.g.,about 95 mol % or higher). The metallocene catalysts, catalyst systemsincorporating such, and processes using such, can produce thisdistribution of dimers with high catalyst efficiency, high productyield, good kinetics as compared to conventional catalysts fordimerizing alpha-olefins.

The metallocene dimer selective reaction is referred to interchangeablyas “first oligomerization” or “first oligomerization process.”

In some embodiments, the metallocene compound useful in the firstoligomerization process for making PAOs can have a structure representedby formula (MC-I):

wherein:

each of R¹, R², and R³ is independently hydrogen, a substituted orunsubstituted linear, branched, or cyclic C₁-C₃₀ (such as C₁-C₂₀, e.g.,a C₁-C₈) hydrocarbyl group;

each of R⁴, R⁵, R⁶, and R⁷ is independently hydrogen, a substituted orunsubstituted linear, branched, or cyclic C₁-C₃₀ (such as a C₁-C₂₀,e.g., a C₁-C₈) hydrocarbyl group, or one or more of R⁴ and R⁵, R⁵ andR⁶, or R⁶ and R⁷, taken together with the carbon atoms in the indenylring to which they are directly connected, collectively form one or moresubstituted or unsubstituted rings fused to the indenyl ring;

each of R⁵, R⁹, R¹⁰, R¹¹, and R¹² is independently a substituted orunsubstituted linear, branched, or cyclic C₁-C₃₀ (such as C₁-C₂₀, e.g.,a C₁-C₈) hydrocarbyl, silylcarbyl, or germanyl group;

M is a transition metal, such as a group 3, 4, or 5 transition metal,such as a group 4 transition metal, such as Hf, Ti, or Zr;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ (e.g., a C₁-C₈) substituted or unsubstituted linear, branched, orcyclic hydrocarbyl group, or optionally two or more X moieties maytogether form a fused ring or ring system; and

m is an integer equal to 1, 2 or 3, such as 2.

In at least one metallocene compound formula herein, each of R¹, R², andR³ can be independently hydrogen or a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, anethyl, a propyl, a butyl, a cyclohexyl, or a phenyl).

In at least one metallocene compound formula herein, each of R¹, R², andR³ can be subject to the proviso that at least one of R¹, R², and R³ isa substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀, suchas C₁-C₈ hydrocarbyl group, such as C₁-C₆ hydrocarbyl group (e.g., amethyl, an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl), and twoof R¹, R², and R³ are each hydrogen. In some embodiments, a first one ofR¹, R², and R³ is a substituted or unsubstituted linear, branched, orcyclic C₁-C₂₀ (such as a C₁-C₈, such as C₁-C₆ hydrocarbyl group, e.g., amethyl, an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl)hydrocarbyl group; a second one of R¹, R², and R³ is hydrogen; and athird one of R¹, R², and R³ is hydrogen, a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₂₀ (such as a C₁-C₈, such as C₁-C₆hydrocarbyl group, e.g., a methyl, an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl) hydrocarbyl group.

In at least one metallocene compound formula herein, each of R¹ and R³can be independently a substituted or unsubstituted linear, branched, orcyclic C₂-C₆ hydrocarbyl group (e.g., an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl), and R² can be a hydrogen. In at least oneembodiment, each of R¹ and R³ can be independently each a methyl groupand R² can be a hydrogen.

In at least one metallocene compound formula herein, one or both of R¹and R³ can be a tertiary or quaternary beta branched ligand in which thealpha and beta atoms are a Group 14 atom, e.g., carbon, silicon,germanium, and two or more, such as three, substituted or unsubstitutedlinear, branched, or cyclic C₁-C₁₈, such as C₁-C₈, hydrocarbyl groupsattached to the beta atom. Examples include neopentyl, betatrialkylsilyl-methyl, and beta-trialkylgermanyl-methyl moieties.

In at least one metallocene compound formula herein, examples of C₁-C₂₀and/or C₁-C₃₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl groups can include: methyl, ethyl, n-propyl, isopropyl,n-butyl, 1-methylpropyl, 1-ethylethyl, n-pentyl, neopentyl(2,2-methylpropyl), 1-methylpentyl, 1-ethylpropyl, 1-hexyl,1-methylpentyl, 1-ethylbutyl, 1-propylpropyl, optionally substitutedcyclohexyl, optionally substituted phenyl, optionally substitutedbenzyl, and the like, and any ethylenically unsaturated group that canbe derived from them by eliminating one available hydrogen group fromeach of two adjacent carbon atoms therein.

In at least one metallocene compound formula herein, M can comprise, canconsist essentially of, or can be Ti, Zr, and/or Hf. In at least oneembodiment, M can comprise, can consist essentially of, or can be Zrand/or Hf, such as Hf In some embodiments, m can be an integer equal to1, 2 or 3, such as 2.

In at least one metallocene compound formula herein, each X can beindependently a halogen or a substituted or unsubstituted linear,branched, or cyclic C₁-C₆ hydrocarbyl group, e.g., a methyl, an ethyl, apropyl, a butyl, a phenyl, a benzyl, a chloride, a bromide, or aniodide, such as methyl.

In at least one metallocene compound formula herein, at least three ofR⁸, R⁹, R¹⁰, R¹¹, and R¹² are not hydrogen. In some embodiments, atleast four of R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each independently asubstituted or unsubstituted linear, branched, or cyclic C₁-C₈hydrocarbyl group, such as methyl or ethyl.

In at least one metallocene compound formula herein, R¹² is asubstituted or unsubstituted linear, branched, or cyclic C₁-C₈hydrocarbyl group, such as methyl or ethyl. In some embodiments, i) atleast three of R⁸, R⁹, R¹⁰, R¹¹, and R¹² if present are not hydrogen,ii) two or more of R⁸, R⁹, R¹⁰, R¹¹, and R¹² if present together form afused ring or ring system; iii) at least two of R⁴, R⁵, R⁶, and R⁷ arehydrogen; iv) each X is independently a halogen or a substituted orunsubstituted linear, branched, or cyclic C₁-C₆ hydrocarbyl group; v) Mcomprises Zr or Hf or a combination thereof.

In at least one metallocene compound formula herein, R⁸, R⁹, R¹⁰, R¹¹,and R¹² are each independently a substituted or unsubstituted linear,branched, or cyclic C₁-C₈ hydrocarbyl group, such as methyl or ethyl.

In at least one metallocene compound formula herein, the metallocenecompound useful in the first oligomerization process for making PAOs canhave a structure represented by formula (MC-II):

wherein:

each of R¹³, R¹⁴, R¹¹, R¹⁶, R¹⁷, and R¹⁸ can be independently hydrogenor a substituted or unsubstituted linear, branched, or cyclic C₁-C₃₀(such as C₁-C₂₀, e.g., a C₁-C₈) hydrocarbyl, silylcarbyl, or germanylgroup; and

each of R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², M, X, m, C₁-C₃₀, andC₁-C₂₀ can be as described above.

In some embodiments, a catalyst compound useful for the firstoligomerization process can include catalyst I.A, catalyst I.B, catalystI.C, or a combination thereof:

In some embodiments, a catalyst compound useful for the firstoligomerization process can include those suitable oligomerizationcatalysts described herein.

In at least one embodiment, the catalyst compound can be part of acatalyst system, and such catalyst systems for the first oligomerizationcan include those suitable oligomerization catalysts described herein.

In at least one embodiment, a process to produce a poly alpha-olefin(PAO) includes introducing a C₄-C₃₂ alpha-olefin (e.g., a C₆-C₃₂alpha-olefin) and a catalyst system comprising an activator and ametallocene compound into a reactor under reactor conditions andobtaining a product comprising PAO dimer, optional higher oligomers ofalpha-olefin, or a combination thereof, the PAO dimer comprising 96 mol% or more of vinylidene based on total moles of vinylidene,disubstituted vinylene, and trisubstituted vinylene in the product, themetallocene compound is represented by formula (MC-I) and/or formula(MC-II).

In at least one embodiment, a first oligomerization process for making apoly alpha-olefin (e.g., a dimer of an alpha-olefin) can includeintroducing an alpha-olefin and a catalyst system into a reactor, e.g.,a polymerization or oligomerization reactor, under reactor conditions toform a product comprising PAO dimer.

In at least one embodiment, the product produced from the firstoligomerization process can include one or more PAO dimer, such asdisubstituted vinylene, trisubstituted vinylene, vinylidene, or acombination thereof. In some embodiments, the product produced from thefirst oligomerization process can include PAO dimers (e.g., vinylidene,disubstituted vinylene, trisubstituted vinylene), trimer ofalpha-olefins (PAO trimer), tetramer of alpha-olefins (PAO tetramer),higher oligomers of alpha-olefins (if any), vinyls, or a combinationthereof.

In at least one embodiment, the first oligomerization process can have aselectivity towards vinylidenes at about 80 mol % or more, such as about85 mol % or more, such as about 88 mol % or more, such as about 90 mol %or more, such as from about 91 mol % to about 100 mol %, such as fromabout 92 mol % to about 99 mol %, such as from about 93 mol % to about98 mol %, such as about 94 mol %, about 95 mol %, about 96 mol %, orabout 97 mol %, based on a total moles of a product produced.

In at least one embodiment, the first oligomerization process can have aselectivity towards products other than vinylidene (e.g., trisubstitutedvinylene, disubstituted vinylene, vinyls, PAO trimer, PAO tetramer,higher oligomers, or a combination thereof) of about 20 mol % or less,such as about 15 mol % or less, such as about 12 mol % or less, such asabout 10 mol % or less, such as from about 0 mol % to about 9 mol %,such as from about 1 mol % to about 8 mol %, such as from about 2 mol %to about 7 mol %, such as about 3 mol %, about 4 mol %, about 5 mol %,or about 6 mol %, based on the total moles of product produced.

In at least one embodiment, the first oligomerization process can have aselectivity towards a PAO trimer of about 20 wt % or less, such as about15 wt % or less, such as about 12 wt % or less, such as about 10 wt % orless, such as from about 0 wt % to about 9 wt %, such as from about 1 wt% to about 8 wt %, such as from about 2 wt % to about 7 wt %, such asabout 3 wt %, about 4 wt %, about 5 wt %, or about 6 wt %, based on thetotal moles of product produced.

In at least one embodiment, the first oligomerization process can have aselectivity towards a PAO tetramer and/or higher oligomers ofalpha-olefins of about 20 wt % or less, such as about 15 wt % or less,such as about 12 wt % or less, such as about 10 wt % or less, such asfrom about 0 wt % to about 9 wt %, such as from about 1 wt % to about 8wt %, such as from about 2 wt % to about 7 wt %, such as about 3 wt %,about 4 mol %, about 5 wt %, or about 6 wt %, based on the total molesof product produced.

In at least one embodiment, the first oligomerization process can forman amount (in weight percent, wt %) of PAO dimer of about 40 wt % ormore, such as from about 45 wt % to about 100 wt %, such as from about50 wt % to about 99 wt %, such as from about 55 wt % to about 98 wt %,such as from about 60 wt % to about 95 wt %, such as from about 65 wt %to about 90 wt %, such as from about 70 wt % to about 85 wt %, such asfrom about 75 wt % to about 85 wt %, based on a total amount of productproduced. In some embodiments, the first oligomerization process canform an amount of PAO dimer of about 80 wt % or more, such as about 81wt % or more, about 82 wt % or more, about 83 wt % or more, about 84 wt% or more, about 85 wt % or more, about 86 wt % or more, about 87 wt %or more, about 88 wt % or more, about 89 wt % or more, about 90 wt % ormore, about 91 wt % or more, about 92 wt % or more, about 93 wt % ormore, about 94 wt % or more, about 95 wt % or more, about 96 wt % ormore, about 97 wt % or more, about 98 wt % or more, about 99 wt % ormore, or about 100 wt %, based on the total amount of product produced.

In at least one embodiment, the first oligomerization process can forman amount of PAO trimer, PAO tetramer, higher oligomers of alpha-olefin,or a combination thereof of about 60 wt % or less, such as from about 0wt % to about 55 wt %, such as from about 1 wt % to about 50 wt %, suchas from about 2 wt % to about 49 wt %, such as from about 5 wt % toabout 40 wt %, such as from about 10 wt % to about 35 wt %, such as fromabout 15 wt % to about 30 wt %, such as from about 20 wt % to about 25wt %, based on a total amount of product produced. In some embodiments,the first oligomerization process can form an amount of PAO trimer, PAOtetramer, higher oligomers of alpha-olefin, or a combination thereof ofabout 20 wt % or less, such as about 0 wt %, about 1 wt % or less, about2 wt % or less, about 3 wt % or less, about 4 wt % or less, about 5 wt %or less, about 6 wt % or less, about 7 wt % or less, about 8 wt % orless, about 9 wt % or less, about 10 wt % or less, about 11 wt % orless, about 12 wt % or less, about 13 wt % or less, about 14 wt % orless, about 15 wt % or less, about 16 wt % or less, about 17 wt % orless, about 18 wt % or less, or about 19 wt % or less, based on thetotal amount of product produced.

In at least one embodiment, the first oligomerization process can forman amount of vinylidene, based on the total moles of PAO dimer produced,of about 50 mol % or more, such as from about 55 mol % to about 100 mol%, such as from about 60 mol % to about 95 mol %, such as from about 65mol % to about 90 mol %, such as from about 70 mol % to about 85 mol %,such as from about 75 mol % to about 80 mol %, where PAO dimer includesvinylidenes, disubstituted vinylene, and trisubstituted vinylene. Insome embodiments, the first oligomerization process can form an amountof vinylidene, based on the total moles of PAO dimer produced, of about80 mol % or more, such as about 81 mol % or more, about 82 mol % ormore, about 83 mol % or more, about 84 mol % or more, about 85 mol % ormore, about 86 mol % or more, about 87 mol % or more, about 88 mol % ormore, about 89 mol % or more, about 90 mol % or more, about 91 mol % ormore, about 92 mol % or more, about 93 mol % or more, about 94 mol % ormore, about 95 mol % or more, about 96 mol % or more, about 97 mol % ormore, about 98 mol % or more, about 99 mol % or more, or about 100 mol%, where PAO dimer includes vinylidenes, disubstituted vinylene, andtrisubstituted vinylene.

In at least one embodiment, the first oligomerization process can forman amount of disubstituted vinylene, trisubstituted vinylene, or acombination thereof, based on the total moles of PAO dimer produced, ofabout 50 mol % or less, such as about 0% to about 45%, such as fromabout 5% to about 40%0, such as from about 10% to about 35%, such asfrom about 15% to about 30%, such as from about 20%0 to about 25%, wherePAO dimer includes vinylidenes, disubstituted vinylene, andtrisubstituted vinylene. In some embodiments, the first oligomerizationprocess can form an amount of disubstituted vinylene, trisubstitutedvinylene, or a combination thereof, based on the total moles of PAOdimer produced, of about 20 mol % or less, such as about 0 mol %, about1 mol % or less, about 2 mol % or less, about 3 mol % or less, about 4mol % or less, about 5 mol % or less, about 6 mol % or less, about 7 mol% or less, about 8 mol % or less, about 9 mol % or less, about 10 mol %or less, about 11 mol % or less, about 12 mol % or less, about 13 mol %or less, about 14 mol % or less, about 15 mol % or less, about 16 mol %or less, about 17 mol % or less, about 18 mol % or less, or about 19 mol% or less, based on the total moles of PAO dimer produced.

In at least one embodiment, the amount of PAO (e.g., dimer, trimer,tetramer, higher oligomers of an alpha olefin, or a combination thereof)produced per gram of catalyst (gPAO/gCat) in the first oligomerizationprocess can be from about 1,000 gPAO/gCat to about to 150,000 gPAO/gCat,such as from about 10,000 gPAO/gCat to about 100,000 gPAO/gCat, such asfrom about 30,000 gPAO/gCat to about 75,000 gPAO/gCat. In at least oneembodiment, the amount of PAO (e.g., dimer, trimer, tetramer, higheroligomers of an alpha olefin, or a combination thereof) produced pergram of catalyst (gPAO/gCat) in the first oligomerization process can befrom about 30,000 gPAO/gCat or more, such as from about 35,000 gPAO/gCatto about 80,000 gPAO/gCat, such as from about 40,000 gPAO/gCat to about75,000 gPAO/gCat, such as from about 45,000 gPAO/gCat to about 70,000gPAO/gCat, such as from about 50,000 gPAO/gCat to about 65,000gPAO/gCat, such as from about 55,000 gPAO/gCat to about 60,000gPAO/gCat.

In at least one embodiment, the amount of conversion in the firstoligomerization of LAO to PAO dimer (e.g., vinylidenes, disubstitutedvinylene, and trisubstituted vinylene, or a combination thereof), PAOtrimer, higher oligomers of alpha-olefin, or a combination thereof canbe greater than about 25%, such as greater than about 75%, such asgreater than about 80%, such as greater than about 85%, such as greaterthan about 90%, such as greater than about 95%, such as greater thanabout 99%.

In at least one embodiment, the LAO can isomerize to branched and/orinternal olefin during the first oligomerization. The amount of suchisomerization can be less than about 5 wt %, such as less than about 3wt %, such as less than about 2 wt %, such as less than about 1.9 wt %,such as less than about 1.5 wt %, such as less than about 1 wt %, suchas less than about 0.9 wt %, such as less than about 0.5 wt %.

In some embodiments, the reactor conditions for the firstoligomerization process can include a mol ratio of catalyst (e.g.,metallocene compound) to activator, an amount of scavenger in thecatalyst batch, an amount of scavenger in LAO, an amount of solvent,reactor temperature, reactor pressure, residence time, and catalystloading.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a mol ratio of catalyst to activatorof from about 0.1:1 to 10:1, such as from about 0.5:1 to about 5:1, suchas from about 0.75:1 to about 3:1, such as from about 1:1.2 to about1:1, such as about 1:1.05, about 1:1.10, or about 1:1.15.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include an amount of scavenger in LAO ofabout 0 ppm or greater, such as about 4 ppm or greater, such as fromabout 5 ppm to about 200 ppm, such as from about 10 ppm to about 190ppm, such as from about 30 ppm to about 170, such as from about 50 ppmto about 150 ppm, such as from about 75 ppm to about 125 ppm. In atleast one embodiment, the reactor conditions for the firstoligomerization process can include an amount of scavenger in LAO ofabout 0 to about 500 ppm; such as from about 0.1 to about 100 ppm, suchas from about 1 to about 20 ppm.

In at least on embodiment, the amount of scavenger in the catalyst batchfor the first oligomerization process can be about 0 wt % or more, suchas from about 0.001 wt % to about 5 wt %, such as from about 0.01 wt %to about 2 wt %, such as from about 0.1 wt % to about 0.5 wt %.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a reactor temperature of from about0° C. to about 300° C., such as from about 10° C. to about 230° C., suchas from about 25° C. to about 200° C., such as from about 100° C. toabout 160° C., such as from about 110° C. to about 155° C., such as fromabout 130° C. to about 148° C., such as from about 135° C. to about 145°C. In some embodiments, the reactor conditions for the firstoligomerization process can include a reactor temperature of about 130°C., about 131° C., about 132° C., about 133° C., about 134° C., about135° C., about 136° C., about 137° C., about 138° C., about 139° C.,about 140° C., about 141° C., about 142° C., about 143° C., about 144°C., about 145° C., about 146° C., about 147° C., or about 148° C. In atleast one embodiment, the reactor conditions for the firstoligomerization process can include a reactor temperature of about 120°C. or more, such as from about 130° C. to about 180° C.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a reactor pressure of from about 1.5psia to about 1,500 psia, such as from about 7 psia to about 1,200 psia,such as from about 15 psia to about 750 psia, such as from about 30 psiato about 100 psia.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a residence time such as less thanabout 72 hours, such as from about 1 minute to about 20 hours, such asfrom about 5 minutes to about 10 hours, such as from about 30 minutes toabout 9 hours, such as from about 1 hour to about 5 hours, such as fromabout 3 hours to about 4 hours. In at least one embodiment, the reactorconditions for the first oligomerization process can include a residencetime of about 24 hours or less, such as about 10 hours or less, such asabout 5 hours or less, such as about 3 hours or less.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a catalyst loading of from about20,000 grams linear alpha-olefin (gLAO) per 1 g Cat (gCat) (gLAO/gCat)to about 150,000 gLAO/gCat, such as 1,000 gLAO/gCat or more, 5,000gLAO/gCat or more, 10,000 gLAO/gCat or more, 20,000 gLAO/gCat or more,such as from about 25,000 gLAO/gCat to about 80,000 gLAO/gCat, such asfrom about 30,000 gLAO/gCat to about 80,000 gLAO/gCat, such as fromabout 35,000 gLAO/gCat to about 75,000 gLAO/gCat, such as from about40,000 gLAO/gCat to about 65,000 gLAO/gCat, such as from about 45,000gLAO/gCat to about 60,000 gLAO/gCat, such as from about 50,000 gLAO/gCatto about 55,000 gLAO/gCat. In at least one embodiment, the reactorconditions for the first oligomerization process can include a catalystloading of from about 40,000 g gLAO/gCat to 80,000 gLAO/gCat, such asfrom about 50,000 gLAO/gCat to about 75,000 gLAO/gCat.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a flow rate of the catalyst systemof greater than about 5 gCat/hr, such as from about 6 gCat/hr to about70 kgCat/hr, such as about 6 gCat/hr to about 10 kgCat/hr, such as about6 gCat/hr to about 1 kgCat/hr, such as about 6 gCat/hr to 50 gCat/hr,such as 6 gCat/hr to 25 gCat/hr, such as from about 7 gCat/hr to about24 gCat/hr, such as from about 8 gCat/hr to about 23 gCat/hr, such asabout 9 gCat/hr, about 10 gCat/hr, about 11 gCat/hr, about 12 gCat/hr,about 13 gCat/hr, about 14 gCat/hr, about 15 gCat/hr, about 16 gCat/hr,about 17 gCat/hr, about 18 gCat/hr, about 19 gCat/hr, about 20 gCat/hr,about 21 gCat/hr, or about 22 gCat/hr.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a flow rate of the alpha-olefin ofgreater than about 100 g/hr, such as from about 200 g/hr to 45,000kg/hr, such as from about 1,000 g/hr to 15,000 kg/hr, such as from about1,500 g/hr to 1,000,000 g/hr, such as from 1,800 g/hr to 10,000 g/hr,such as about 1,900 g/hr, such as about 2,080 g/hr.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a flow rate of the alpha-olefin ofabout 100 grams alpha-olefin per hour (ghr) or more, such as from about150 g/hr to about 7,500 g/hr, such as from about 300 g/hr to about 3,000g/hr, such as from about 500 g/hr to about 2,000 g/hr, such as fromabout 750 g/hr to about 1,500 g/hr.

In at least one embodiment, the reactor conditions for the firstoligomerization process can include a flow rate of the alpha-olefin ofabout 100 grams alpha-olefin per hour (ghr also written as g/hr) ormore, such as 1,000 g/hr or more, such as 10,000 g/hr or more, such as100,000 g/hr or more, such as 200,000 g/hr or more, such as 300,000 g/hror more, such as 400,000 g/hr or more.

In at least one embodiment, the first oligomerization process caninclude a PAO dimer selectivity (in weight ratio) of about 60% or morewith at least one of the following conditions: (i) at a catalystproductivity of about 10,000 gPAO/gCat or more (such as about 10,000 toabout 100,000 gPAO/gCat) without the use of alumoxane; (ii) at acatalyst productivity of about 10,000 gPAO/gCat or more (such as about10,000 to about 100,000 gPAO/gCat) without the use of alumoxane noraluminum alkyl; (iii) at a catalyst productivity of about 10,000gPAO/gCat or more (such as about 10,000 to about 100,000 gPAO/gCat) withabout 500 ppm or less of an aluminum alkyl; (iv) at a catalystproductivity of about 10,000 gPAO/gCat or more (such as about 10,000 toabout 100,000 gPAO/gCat) with about 20 ppm or less of an aluminum alkyl;(v) at a catalyst productivity of about 10,000 gPAO/gCat or more (suchas about 10,000 to about 100,000 gPAO/gCat) with a residence time ofabout 24 hours or less; (vi) at a catalyst productivity of about 10,000gPAO/gCat or more (such as about 10,000 to about 100,000 gPAO/gCat) witha residence time of about 10 hours or less; or (vii) at a catalystproductivity of about 30,000 gPAO/gCat or more (such as about 30,000 toabout 100,000 gPAO/gCat) with a residence time of about 10 hours orless. The PAO dimer selectivity is based on a weight ratio of PAOdimer/(PAO dimer+PAO trimer+PAO tetramer+heavier oligomers of LAO).

In at least one embodiment, the first oligomerization process caninclude a PAO dimer selectivity (in weight ratio) of about 85% or morewith at least one of the following conditions: (i) at a catalystproductivity of about 30,000 gPAO/gCat or more (such as about 30,000 toabout 100,000 gPAO/gCat) with a residence time of about 10 hours orless; (ii) at a catalyst productivity of about 30,000 gPAO/gCat or more(such as about 30,000 to about 100,000 gPAO/gCat) with a residence timeof about 5 hours or less; or (iii) at a catalyst productivity of about50,000 gPAO/gCat or more (such as about 50,000 to about 100,000gPAO/gCat) with a residence time of about 5 hours or less. The PAO dimerselectivity is based on a weight ratio of PAO dimer/(PAO dimer+PAOtrimer+PAO tetramer+heavier oligomers of LAO).

In at least one embodiment, the first oligomerization process caninclude a PAO dimer selectivity (in weight ratio) of about 90% or morewith at least one of the following conditions: (i) at a catalystproductivity of about 50,000 gPAO/gCat or more (such as about 50,000 toabout 100,000 gPAO/gCat) with a residence time of about 10 hours orless; (ii) at a catalyst productivity of about 50,000 gPAO/gCat or more(such as about 50,000 to about 100,000 gPAO/gCat) with a residence timeof about 5 hours or less; (iii) at a catalyst productivity of about60,000 gPAO/gCat or more (such as about 60,000 to about 100,000gPAO/gCat) with a residence time of about 5 hours or less; (iv) at acatalyst productivity of about 60,000 gPAO/gCat or more (such as about60,000 to about 100,000 gPAO/gCat) with a residence time of about 3hours or less; or (v) at a catalyst productivity of about 65,000gPAO/gCat or more (such as about 65,000 to about 100,000 gPAO/gCat) witha residence time of about 3 hours or less. The PAO dimer selectivity isbased on a weight ratio of PAO dimer/(PAO dimer+PAO trimer+PAOtetramer+heavier oligomers of LAO).

In at least one embodiment, the reactor conditions for the firstoligomerization process can include one or more of the followingconditions: a mol ratio of catalyst:activator of about 1:1.05 in about390 g toluene with about 10 ppm to about 12 ppm TNOA; the activator isN,N-dimethylanilinium tetrakis (pentafluorophenyl)borate; analpha-olefin (LAO) flow rate of about 2080 g/hr; a catalyst loading ofabout 65,000 gLAO/gCat; a catalyst system flow rate of about 0.24 mL/min(12.7 g/hr); an amount of TNOA as scavenger in LAO of about 55 ppm; atemperature of from about 130° C. to about 148° C.; and a residence timeof about 3 hours.

In at least one embodiment, the alpha-olefin in the feed for the firstoligomerization process can be one or more C₂-C₃₂ alpha-olefins, such asC₄-C₃₂ alpha-olefins, such as C₆-C₃₀ alpha-olefins, such as C₆-C₂₄alpha-olefins, such as C₆-C₁₈ alpha-olefins, C₈-C₁₈ alpha-olefins, C₆ toC₁₆ alpha-olefins, C₆-C₁₂ alpha-olefins, or a combination thereof.Non-limiting examples of alpha-olefins include 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, anda combination thereof. Various suitable alpha-olefins (e.g., linearalpha-olefins) and their characteristics that can be used for the firstoligomerization process are discussed below in suitable sections ofSection IV.

In at least one embodiment, hydrogen is optionally added to the reactorat a concentration of 0 to 100 psi; such as from 0 to 50 psi, such asfrom 5-10 psi.

In at least one embodiment, the heavy oligomers (degree ofoligomerization of at least 3) are hydrogenated to create a finished PAOlubricant. In at least one embodiment, the kinematic viscosity at 100°C. of at least a portion of the hydrogenated first reactor effluent(e.g., the trimer) can be less than 5 cSt, such as less than 3.5 cSt.

In at least one embodiment, the Noack volatility of at least a portionof the hydrogenated first reactor effluent (e.g., the trimer) can beless than 15 wt %, such as less than 13 wt %.

In at least one embodiment, the rotating pressure vessel oxidation test(RPVOT) of at least a portion of the hydrogenated first reactor effluent(e.g., the trimer) can be greater than 40 minutes, such as greater than60 minutes, such as greater than 75 minutes.

Embodiments for feed purification, the first oligomerization reaction,and the catalyst system for the first oligomerization reaction may befound in suitable sections of Section IV. Other parameters for theselectivity and yield of products produced from the firstoligomerization reaction may be found in suitable sections of SectionIV.

II. Process for Producing PAO Trimers from PAO Dimers

The present disclosure also includes processes using metallocenecatalysts to improve yields for producing PAO trimer, such as a lowviscosity PAO trimer. Conventional methods of forming PAO trimersinvolve a reaction of a PAO dimer feedstock made from an oligomerizationprocess that contains a significant amount of disubstituted vinylene aswell as PAO trimer, PAO tetramer, and higher oligomers of alpha-olefin.The disubstituted vinylene, however, is not highly reactive when addedto a second oligomerization process (e.g., a BF₃ catalyzed process), andthe reaction kinetics are very slow. In addition, the unreacted dimer inthe stream going into the BF₃ catalyzed conventional reactorcontaminates the stream produced out of the BF₃ process and reduces thevalue of that by-product.

The inventors have found that reducing (or eliminating) the amount ofdisubstituted vinylene in the PAO dimer feedstock from the firstoligomerization process can provide production of a PAO trimer productat higher yields and higher purity than conventional processes. Inaddition, the higher purity intermediate PAO (e.g., the PAO dimerfeedstock) produced from the first oligomerization process (having loweramounts of PAO trimer, lower amounts of PAO tetramer, and lower amountsof higher oligomers of alpha-olefin relative to conventional PAO dimerfeedstocks) provides the production of high amounts of PAO trimer fromthe second oligomerization process.

The PAO produced from the first oligomerization process described abovein Section I can include dimer (such as vinylidene dimers), trimer,optionally tetramer and higher oligomers of the respective alpha-olefinfeedstocks, or a combination thereof. This PAO produced from the firstoligomerization process described above is referred to interchangeablyas “intermediate PAO” and “first reactor effluent.” The oligomerizationprocess described in Section I above can be performed in a firstreactor, e.g., a metallocene reactor. The PAO produced from the secondoligomerization process is referred to interchangeably as “hybridtrimer,” “hybrid dimer” and “second reactor effluent.” The secondoligomerization may be performed in a second reactor, and the secondreactor may include one or more sub-reactors.

The hybrid process is referred to interchangeably as “secondoligomerization process” or “second oligomerization.”

The intermediate PAO (e.g., the PAO dimer feedstock) may be used as thesole olefin feedstock to the second oligomerization process or may beused together with an alpha-olefin feedstock of the type used as theolefin starting material for the first oligomerization process. Otherportions of the effluent from the first oligomerization process may alsobe used as a feedstock to the second oligomerization process, includingunreacted LAO. Alpha-olefins with the same attributes as those used forthe first oligomerization process may be used for the secondoligomerization. Typical ratios for the PAO dimer portion of theintermediate PAO to the alpha-olefins fraction of the intermediate PAOcan be from about 90:10 to about 10:90, such as from about 80:20 toabout 20:80 by weight. In at least one embodiment, the PAO dimer of theintermediate PAO can make up about 50 mol % of the olefinic feedmaterial since the properties and distribution of the final product,dependent in part upon the starting material, can be favorably affectedby feeding the intermediate PAO at an equimolar ratio with thealpha-olefins.

In at least one embodiment, the feed for second oligomerization processcan have a distribution of PAO dimer, PAO trimer, PAO tetramer, higheroligomers of alpha-olefin, or a combination thereof, can have the samedistribution of effluent produced in the metallocene dimer selectiveprocess described in Section I. In at least one embodiment, the feed forthe second oligomerization reactor is a product from the metallocenedimer selective process described in Section I.

The PAO dimer of the intermediate PAO can possess at least onecarbon-carbon unsaturated double bond. Portions of the PAO dimer caninclude vinylidene dimers, disubstituted vinylenes, trisubstitutedvinylenes, and a combination thereof. The distribution of vinylidenedimers, disubstituted vinylenes, trisubstituted vinylenes, and acombination thereof in the PAO dimer can be the distribution asdescribed above.

The structure of the intermediate PAO can be such that, when reacted ina second oligomerization, the intermediate PAO can react with theoptional LAO to form a “hybrid trimer” at high yields. This allows forhigh conversion and yield rates of the PAO products. In at least oneembodiment, the PAO product from the second oligomerization comprisesprimarily a hybrid trimer formed from the dimer and the respective LAOfeedstock.

Any suitable oligomerization process and acid catalyst composition maybe used for the second oligomerization process. A catalyst for thesecond oligomerization can be a non-transition metal catalyst. Acatalyst can be a Lewis acid catalyst. U.S. Patent Publication Nos.2009/0156874 and 2009/0240012 describe a process that can be used forthe second oligomerization, to which reference is made for details offeedstocks, compositions, catalysts and co-catalysts, and processconditions. The Lewis acid catalysts of US 2009/0156874 and US2009/0240012 include the metal and metalloid halides conventionally usedas Friedel-Crafts catalysts, and examples include AlCl₃, BF₃, AlBr₃,TiCl₃, and TiCl₄ either alone or with a protic promoter/activator. Borontrifluoride is commonly used but not particularly suitable unless it isused with a protic promoter. Useful co-catalysts are well known anddescribed in detail in US 2009/0156874 and US 2009/0240012. Solid Lewisacid catalysts, such as synthetic or natural zeolites, acid clays,polymeric acidic resins, amorphous solid catalysts such assilica-alumina, and heteropoly acids such as the tungsten zirconates,tungsten molybdates, tungsten vanadates, phosphotungstates andmolybdotungstovanadogermanates (e.g., WOx/ZrO₂, WOx/MoO₃) may also beused although these are not generally as favored economically.Additional process conditions and other details are described in detailin US 2009/0156874 and US 2009/0240012, and incorporated herein byreference.

In at least one embodiment, the second oligomerization can be performedin the presence of BF₃ and at least one activator such as an alcohol, orthe second oligomerization can be performed in the presence of BF₃ andat least two different activators selected from alcohols and alkylacetates. The alcohols can be C₁ to C₁₀ alcohols and the alkyl acetatesare C₁ to C₁₀ alkyl acetates. For example, both co-activators are C₁ toC₆ based compounds. Two example combinations of co-activators can be i)ethanol and ethyl acetate and ii) n-butanol and n-butyl acetate. Theratio of alcohol to alkyl acetate can be from about 0.2 to about 15,such as about 0.5 to about 7.

Temperatures for the second oligomerization in the second reactor can befrom about 0° C. to about 60° C., such as from about 10° C. to about 55°C., such as from about 20° C. to about 40° C., from about 10° C. toabout 40° C., or from about 15° C. to about 25° C. In at least oneembodiment, the temperatures for the second oligomerization in thesecond reactor can be less than about 32° C., such as from about 15° C.to about 30° C., such as from about 20° C. to about 25° C.

In at least one embodiment, the acid catalyst composition loading forthe second oligomerization can be from about 0.5 mmol per 100 g LAO(mmolCat/100 gLAO) to about 30 mmolCat/100 gLAO, such as from about 5mmolCat/100 gLAO to about 15 mmolCat/100 gLAO, such as from about 6mmolCat/100 gLAO to about 14 mmolCat/100 gLAO, such as about 8mmolCat/100 gLAO, about 10 mmolCat/100 gLAO, or about 12 mmolCat/100gLAO.

In at least one embodiment, the LAO feedstock for the secondoligomerization (as well as the first oligomerization) can be one ormore C₂-C₃₂ alpha-olefins, such as a C₄-C₃₂ alpha-olefin, C₆-C₃₀alpha-olefin, such as a C₆-C₂₄ alpha-olefin, such as a C₆-C₁₈alpha-olefin, a C₈-C₁₈ alpha-olefin, a C₆ to C₁₆ alpha-olefin, or aC₆-C₁₂ alpha-olefin, or a combination thereof. Non-limiting examples ofLAOs can be 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-octadecene, 1-icocene, C₂₂, C₂₄, C₂₆,C₂₈, C₃₀, and C₃₂ LAOs, and a combination thereof. Other suitablealpha-olefin monomers for the second oligomerization can be found inSection IV.

In at least one embodiment, a molar ratio of the PAO dimer of theintermediate PAO to LAO for the second oligomerization process can beabout 1:1 or greater, such as from about 1.5 to about 10:1, such as fromabout 2:1 to about 5:1, such as from about 3:1 to about 4:1. In at leastone embodiment, a molar ratio of the PAO dimer of the intermediate PAOto LAO for the second oligomerization process can be from about 0.1:1 toabout 10:1, such as from about 0.5 to about 5:1, such as from about0.5:1 to about 3:1, such as from about 0.8:1 to about 1.2:1, such asfrom about 0.9:1 to about 1.1:1.

In at least one embodiment, the reactor conditions for the secondoligomerization can include a reactor pressure of from about 10 psia toabout 35 psia, such as from about 15 psia to about 25 psia, such as fromabout 19 psia to about 21 psia.

In at least one embodiment, the second oligomerization can be carriedout in two reactors in series, such as two continuous stirred tankreactors (CSTRs) in series. In some embodiments, the residence time inthe first reactor of the second oligomerization can be from about 0.25hour to about 5 hours, such as from about 0.5 hour to about 3 hours, andthe residence time in the second reactor of the second oligomerizationcan be from about 0.25 hour to about 5 hours, such as from about 0.5hour to about 3 hours.

In at least one embodiment, the second oligomerization can be carriedout in one reactor such as a CSTR. In some embodiments, the residencetime in the reactor for the second oligomerization can be from about 1minutes to 10 hour, such as from about 1 hour to about 7 hours, such asfrom about 1 hour to about 2 hours.

Table 1 shows non-limiting types of the PAO product (the hybrid trimer)that can be produced from the second oligomerization process of a PAOdimer with the LAO monomer.

TABLE 1 C6 C8 C9 C10 C12 C14 C16 C6 dimer C18 C20 C21 C22 C24 C26 C28 C8dimer C22 C24 C25 C26 C28 C30 C32 C9 dimer C24 C26 C27 C28 C30 C32 C34C10 dimer C26 C28 C29 C30 C32 C34 C36 C12 dimer C30 C32 C33 C34 C36 C38C40 C14 dimer C34 C36 C37 C38 C40 C42 C44 C16 dimer C38 C40 C41 C42 C44C46 C48

In at least one embodiment, where the LAO feedstock for the firstoligomerization and the second oligomerization processes is the same,the incorporation of PAO dimer of the intermediate PAO into hybridtrimer, tetramer, higher oligomers, or a combination thereof can beabout 75% or more, such as about 80% or more, such as about 85% or more,such as about 90% or more, such as about 95% or more, such as about 99%or more; the conversion of the LAO can be about 75% or more, such asabout 80% or more, such as about 85% or more, such as about 90% or more,such as about 95% or more, such as about 99% or more, and/or the yield %of about 75% or more, such as about 80% or more, such as about 85% ormore, such as about 90% or more, such as about 95% or more, such asabout 99% or more.

In at least one embodiment, where the LAO feedstock for the firstoligomerization and the second oligomerization processes is different,the incorporation of PAO dimer of the intermediate PAO into hybridtrimer, tetramer, higher oligomers, or a combination thereof can beabout 75% or more, such as about 80% or more, such as about 85% or more,such as about 90% or more, such as about 95% or more, such as about 99%or more; the conversion of the LAO can be about 75% or more, such asabout 80% or more, such as about 85% or more, such as about 90% or more,such as about 95% or more, such as about 99% or more; and/or the yield %of about 75% or more, such as about 80% or more, such as about 85% ormore, such as about 90% or more, such as about 95% or more, such asabout 99% or more.

In at least one embodiment, the yield % of PAO trimer in the secondreactor effluent is about 60 wt % or more, such as about 70 wt % ormore, such as about such as about 75 wt % or more, such as about 76 wt %or more, such as about 77 wt % or more, such as about 78 wt % or more,79 wt % or more, such as about 80 wt % or more, such as about 81 wt % ormore, such as about 82 wt % or more, such as about 83 wt % or more, suchas about 84 wt % or more, such as about 85 wt % or more, such as about86 wt % or more, such as about 87 wt % or more, such as about 88 wt % ormore, such as about 89 wt % or more, such as about 90 wt % or more, suchas about 91 wt % or more, such as about 92 wt % or more, such as about93 wt % or more, such as about 94 wt % or more, such as about 95 wt % ormore, such as about 96 wt % or more, such as about 97 wt % or more, suchas about 98 wt % or more, such as about 99 wt % or more, such as about100 wt %, based on a total moles of PAO dimer, PAO trimer, PAO tetramer,and higher oligomers of alpha-olefin in the second reactor effluent.

In at least one embodiment, the second oligomerization process can havea selectivity towards hybrid trimer of about 60 wt % or more, such asabout 70 wt % or more, such as about 75 wt % or more, such as about 76wt % or more, such as about 77 wt % or more, such as about 78 wt % ormore, 79 wt % or more, such as about 80 wt % or more, such as about 81wt % or more, such as about 82 wt % or more, such as about 83 wt % ormore, such as about 84 wt % or more, such as about 85 wt % or more, suchas about 86 wt % or more, such as about 87 wt % or more, such as about88 wt % or more, such as about 89 wt % or more, such as about 90 wt % ormore, such as about 91 wt % or more, such as about 92 wt % or more, suchas about 93 wt % or more, such as about 94 wt % or more, such as about95 wt % or more, such as about 96 wt % or more, such as about 97 wt % ormore, such as about 98 wt % or more, such as about 99 wt % or more, suchas about 100 wt %, based on a total moles of PAO dimer, PAO trimer, PAOtetramer, and higher oligomers of alpha-olefin in the second reactoreffluent.

In at least one embodiment, the yield % of PAO dimer, PAO tetramer,higher oligomers of alpha-olefin, or a combination thereof, in thesecond reactor effluent can be about 40 wt % or less, such as about 30wt % or less, such as about 25 wt % or less, such as about 24 wt % orless, such as about 23 wt % or less, such as about 22 wt % or less, suchas about 21 wt % or less, such as about 20 wt % or less, such as about19 wt % or less, such as about 18 wt % or less, such as about 17 wt % orless, such as about 16 wt % or less, such as about 15 wt % or less, suchas about 14 wt % or less, such as about 13 wt % or less, such as about12 wt % or less, such as about 11 wt % or less, such as about 10 wt % orless, such as about 9 wt % or less, such as about 8 wt % or less, suchas about 7 wt % or less, such as about 6 wt % or less, such as about 5wt % or less, such as about 4 wt % or less, such as about 3 wt % orless, such as about 2 wt % or less, such as about 1 wt % or less, suchas about 0 wt %, based on a total weight of PAO dimer, PAO trimer, PAOtetramer, and higher oligomers of alpha-olefin in the second reactoreffluent.

In at least one embodiment, the second oligomerization process can havea selectivity towards PAO dimer, PAO tetramer, higher oligomers ofalpha-olefin, or a combination thereof, of about 40 mol % or less, suchas about 30 mol % or less, such as about 25 mol % or less, such as about24 mol % or less, such as about 23 mol % or less, such as about 22 mol %or less, such as about 21 mol % or less, such as about 20 mol % or less,such as about 19 mol % or less, such as about 18 mol % or less, such asabout 17 mol % or less, such as about 16 mol % or less, such as about 15mol % or less, such as about 14 mol % or less, such as about 13 mol % orless, such as about 12 mol % or less, such as about 11 mol % or less,such as about 10 mol % or less, such as about 9 mol % or less, such asabout 8 mol % or less, such as about 7 mol % or less, such as about 6mol % or less, such as about 5 mol % or less, such as about 4 mol % orless, such as about 3 mol % or less, such as about 2 mol % or less, suchas about 1 mol % or less, such as about 0 mol %, based on a total molesof PAO dimer, PAO trimer, PAO tetramer, and higher oligomers ofalpha-olefin in the second reactor effluent.

In at least one embodiment, the trimer has an A-A-B structure, where Aand B are different alpha-olefins.

In at least one embodiment, the monomer can be optional as a feedstockin the second reactor (e.g., an oligomerization reactor). In someembodiments, the first reactor effluent comprises unreacted monomer, andthe unreacted monomer can be fed to the second reactor. In someembodiments, monomer can be fed into the second reactor, and the monomercan be an LAO selected from the group including 1-hexene, 1-octene,1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene. In someembodiments, the PAO produced in the second oligomerization can bederived from the PAO dimer portion of the intermediate PAO plus only onemonomer to form one or more trimers. In some embodiments, the PAOproduced in the second oligomerization can be derived from the PAO dimerof the intermediate PAO plus two or more monomers, or three or moremonomers, or four or more monomers, or even five or more monomers. Forexample, the PAO dimer plus a C₈, C₁₀, C₁₂-LAO mixture, or a C₆, C₇, C₈,C₉, C₁₀, C11, C₁₂, C₁₃, C₁₄-LAO mixture, or a C₄, C₆, C₈, C₁₀, C₁₀, C₁₂,C₁₄, C₁₆, C₁₈-LAO mixture can be used as a feed to form trimers.

In at least one embodiment, the second reactor effluent may containtrace amounts of transition metal compound if the catalyst in the firstor subsequent oligomerization is a metallocene catalyst. A trace amountof transition metal compound may be any amount of transition metalcompound or Group 4 metal present in the PAO. Presence of Group 4 metalmay be detected at the ppm or ppb level by ASTM 5185.

In at least one embodiment, the second reactor effluent or a portion ofthe second reactor effluent is hydrogenated to a Bromine number lessthan 2.

In at least one embodiment, the kinematic viscosity at 100° C. of thesecond reactor effluent or a portion of the second reactor effluent(e.g., the hybrid trimer) can be less than about 10 cSt, such as lessthan about 6 cSt, such as less than about 4.5 cSt, such as less thanabout 3.2 cSt, such as from about 2.8 cSt to about 4.5 cSt. In someembodiments, the second reactor effluent or a portion of the secondreactor effluent is hydrogenated to form a hydrogenated second reactoreffluent having a kinematic viscosity at 100° C. less than about 10 cSt,such as less than about 6 cSt, such as less than about 4.5 cSt, such asless than about 3.2 cSt, such as from about 2.8 cSt to about 4.5 cSt.

In at least one embodiment, the kinematic viscosity at 40° C. of thesecond reactor effluent or a portion of the second reactor effluent canbe less than about 25 cSt, such as less than about 15 cSt. In someembodiments, the second reactor effluent or a portion of the secondreactor effluent is hydrogenated to form a hydrogenated second reactoreffluent having a kinematic viscosity at 40° C. of the second reactoreffluent or a portion of the second reactor effluent can be less thanabout 25 cSt, such as less than about 15 cSt.

In at least one embodiment, the pour point of the second reactoreffluent or a portion of the second reactor effluent can be below about−30° C., such as below about −40° C., such as below about −50° C., suchas below about −60° C., such as below about −70° C., such as below about−80° C. In some embodiments, the second reactor effluent or a portion ofthe second reactor effluent is hydrogenated to form a hydrogenatedsecond reactor effluent having a pour point of the second reactoreffluent or a portion of the second reactor effluent can be below about−30° C., such as below about −40° C., such as below about −50° C., suchas below about −60° C., such as below about −70° C., such as below about−80° C.

In at least one embodiment, the Noack volatility of the second reactoreffluent or a portion of the second reactor effluent can be less thanabout 19 wt %, such as less than about 14 wt %, such as less than about12 wt %, such as less than about 10 wt %, such as less than about 9.0 wt%, such as less than about 8.5 wt %, such as less than about 8.0 wt %,such as less than about 7.5 wt %. In some embodiments, the secondreactor effluent or a portion of the second reactor effluent ishydrogenated to form a hydrogenated second reactor effluent having aNoack volatility of the second reactor effluent or a portion of thesecond reactor effluent can be less than about 19 wt %, such as lessthan about 14 wt %, such as less than about 12 wt %, such as less thanabout 10 wt %, such as less than about 9.0 wt %, such as less than about8.5 wt %, such as less than about 8.0 wt %, such as less than about 7.5wt %.

In at least one embodiment, the viscosity index of the second reactoreffluent or a portion of the second reactor effluent can be more thanabout 120, such as more than about 121, such as more than about 125,such as more than about 130, such as more than about 135, such as morethan about 136. In some embodiments, the second reactor effluent or aportion of the second reactor effluent is hydrogenated to form ahydrogenated second reactor effluent having a viscosity index of thesecond reactor effluent or a portion of the second reactor effluent canbe more than about 120, such as more than about 121, such as more thanabout 125, such as more than about 130, such as more than about 135,such as more than about 136.

In at least one embodiment, the cold crank simulator value (CCS) at −35°C. of the second reactor effluent or a portion of the second reactoreffluent may be not more than about 1200 cP, such as not more than about1000 cP, such as not more than about 900 cP. In some embodiments, thesecond reactor effluent or a portion of the second reactor effluent ishydrogenated to form a hydrogenated second reactor effluent having acold crank simulator value (CCS) at −35° C. of the second reactoreffluent or a portion of the second reactor effluent may be not morethan about 1200 cP, such as not more than about 1000 cP, such as notmore than about 900 cP.

In at least one embodiment, the second reactor effluent or a portion ofthe second reactor effluent can have a Brookfield viscosity at 40° C. ofless than about 3000 cP, such as less than about 2000 cP, such as lessthan about 1500 cP. In some embodiments, the second reactor effluent ora portion of the second reactor effluent is hydrogenated to form ahydrogenated second reactor effluent having a Brookfield viscosity at40° C. of less than about 3000 cP, such as less than about 2000 cP, suchas less than about 1500 cP.

In at least one embodiment, the second reactor effluent or a portion ofthe second reactor effluent can have a rotating pressure vesseloxidation test (RPVOT) of about 70 minutes or more, such as about 80minutes or more, such as about 90 minutes or more, such as about 100minutes or more. In some embodiments, the second reactor effluent or aportion of the second reactor effluent is hydrogenated to form ahydrogenated second reactor effluent having a rotating pressure vesseloxidation test (RPVOT) of about 70 minutes or more, such as about 80minutes or more, such as about 90 minutes or more, such as about 100minutes or more.

In at least one embodiment, the second reactor effluent or a portion ofthe second reactor effluent can have a kinematic viscosity at 100° C. ofnot more than about 3.2 cSt and a Noack volatility of not more thanabout 19 wt %. In at least one embodiment, the second reactor effluentor a portion of the second reactor effluent can have a kinematicviscosity at 100° C. of not more than about 3.6 cSt and a Noackvolatility of not more than about 13.0 wt %. In some embodiments, thesecond reactor effluent or a portion of the second reactor effluent ishydrogenated to form a hydrogenated second reactor effluent having akinematic viscosity at 100° C. of not more than about 3.2 cSt and aNoack volatility of not more than about 19 wt %. In at least oneembodiment, the second reactor effluent or a portion of the secondreactor effluent is hydrogenated to form a hydrogenated second reactoreffluent having have a kinematic viscosity at 100° C. of not more thanabout 3.6 cSt and a Noack volatility of not more than about 13.0 wt %.

Functionalized PAOs and Uses of Functionalized PAOs

PAO products (e.g., unhydrogenated LAO dimers and trimers) of thepresent disclosure can be functionalized with one or more reactants (andcan be optionally hydrogenated) through various chemical reactions toproduce a functionalized PAO product. For example, PAOs of the presentdisclosure that have been functionalized (and optionally hydrogenated)may be used in gear oils, industrial oils, hydraulic oils, compressoroils, or in a driveline or electric vehicle fluid.

PAOs prepared herein may be functionalized by reacting a heteroatomcontaining group with the PAO with or without a catalyst. Examplesinclude catalytic hydrosilylation, ozonolysis, hydroformylation, orhydroamination, sulfonation, halogenation, hydrohalogenation,hydroboration, epoxidation, or Diels-Alder reactions with polar dienes,Friedel-Crafts reactions with polar aromatics, maleation with activatorssuch as free radical generators (e.g. peroxides). The functionalizedPAO's can be used in oil additives, as anti-fogging or wettingadditives, surfactants for soaps, detergents, fabric softeners,antistatics, and many other applications. Preferred uses includeadditives for lubricants and or fuels, preferably where the heteroatomcontaining group includes one or more of amines, aldehydes, alcohols,acids, anhydrides, sulphonates, particularly succinic acid, maleic acidand maleic anhydride.

In some embodiments the PAO's produced herein are functionalized asdescribed in U.S. Pat. No. 6,022,929; A. Toyota, T. Tsutsui, and N.Kashiwa, Polymer Bulletin, v. 48, pp. 213-219, 2002; and J. Am. Chem.Soc., 1990, v. 112, pp. 7433-7434. In some embodiments thefunctionalized PAO's produced herein are further functionalized(derivatized), such as described in U.S. Pat. No. 6,022,929; A. Toyota,T. Tsutsui, and N. Kashiwa, Polymer Bulletin, v. 48, pp. 213-219, 2002;J. Am. Chem. Soc., 1990, v. 112, pp. 7433-7434; and WO 2009/155472.

In preferred embodiments, the PAO's of the present disclosure can befunctionalized (e.g. chemically modified with one or more functionalgroups (also referred to as a heteroatom containing group) typicallycontaining heteroatoms such as P, O, S, N, Br, Cl, F, I and or Br(preferably N, O, Cl and or Br, preferably N and or O). Preferredfunctional groups are selected from the group consisting of acids,esters, anhydrides, acid-esters, oxycarbonyls, carbonyls, formyls,formylcarbonyls, hydroxyls, and acetyl halides. Particularly preferredfunctional groups include those represented by the formula: —C(O)—X,where the O is double bonded to the C and the X is hydrogen, nitrogen,hydroxy, oxyhydrocarbyl (e.g. ester), oxygen, the salt moiety —OMwherein M is a metal, e.g. alkali, alkaline earth, transition metal,copper, zinc and the like, oxyhetero, e.g. —O—Z wherein Z represents aheteroatom such as phosphorus boron, sulfur, which heteroatom may besubstituted with hydrocarbyl or oxyhydrocarbyl groups, or two acylgroups may be joined through (X).

Preferred heteroatom containing groups include acyl groups derived frommonounsaturated mono- or dicarboxylic acids and their derivatives, e.g.esters and salts.

More specifically, PAO's functionalized with mono- or dicarboxylic acidmaterial, i.e., acid, anhydride, salt or acid ester are preferred,including the reaction product of the PAO with a monounsaturatedcarboxylic reactant comprising at least one member selected from thegroup consisting of (i) monounsaturated C₄ to C₁₀ dicarboxylic acid(preferably wherein (a) the carboxyl groups are vicinyl, (i.e. locatedon adjacent carbon atoms) and (b) at least one, preferably both, of saidadjacent carbon atoms are part of said monounsaturation); (ii)derivatives of (i) such as anhydrides or C₁ to C₅ alcohol derived mono-or diesters of (i); (iii) monounsaturated C₃ to C₁₀ monocarboxylic acidwherein the carbon-carbon double bond is conjugated to the carboxylgroup, i.e., of the structure —C═C—C(O)— (where O is double bonded toC), and (iv) derivatives of (iii) such as C₁ to C₅ alcohol derivedmonoesters of (iii). Upon reaction with the PAO, the double bond of themonounsaturated carboxylic reactant becomes saturated. Thus, forexample, maleic anhydride reacted with the PAO becomes succinicanhydride, and acrylic acid becomes a propionic acid.

Suitable unsaturated acid materials thereof which are useful functionalcompounds, include acrylic acid, crotonic acid, methacrylic acid, maleicacid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid,chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid,sorbic acid, 3-hexenoic acid, 10-decenoic acid,2-pentene-1,3,5-tricarboxylic acid, cinnamic acid, and lower alkyl (e.g.C₁ to C₄ alkyl) acid esters of the foregoing, e.g. methyl maleate, ethylfumarate, methyl fumarate, etc. Particularly preferred are theunsaturated dicarboxylic acids and their derivatives, especially maleicacid, fumaric acid and maleic anhydride.

Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferablyfrom about 1.0 to about 2.0, and most preferably from about 1.1 to about1.7 moles of said monounsaturated carboxylic reactant are charged to thereactor per mole of PAO charged.

Functionalization can be achieved by any suitable method. Useful methodsinclude the reaction of an olefinic bond of the PAO with an unsaturated,preferably a monounsaturated, carboxylic reactant. Alternatively, theoligomer can be halogenated using chlorine or bromine-containingcompounds. The halogenated PAO can then be reacted with themonounsaturated carboxylic acid. The PAO and the monounsaturatedcarboxylic reactant can also be contacted at elevated temperatures tocause a thermal “ene” reaction to take place. Alternatively, themonounsaturated carboxylic acid can be reacted with the PAO by freeradical induced grafting. The PAO of the present disclosure can befunctionalized by contact with a hydroxy aromatic compound in thepresence of a catalytically effective amount of at least one acidicalkylation catalyst. The alkylated hydroxy aromatic compound can then befurther reacted to form a derivative by Mannich Base condensation withan aldehyde and an amine reagent to yield a Mannich Base condensate. Inyet another means to functionalize the PAO, the PAO may be contactedwith carbon monoxide in the presence of an acid catalyst under Kochreaction conditions to yield the PAO substituted with carboxylic acidgroups. In addition to the above methods of functionalization, the PAOof the present disclosure can be functionalized by methods of airoxidation, ozonolysis, hydroformylation, epoxidation andchloroamination. (For more information please see U.S. Pat. No.6,022,929 Column 21, line 16 to column 33, line 27.)

The polyalpha-olefins produced herein contain one or more unsaturateddouble bonds, rich in vinylidene content with some 1,2-disubstitutedolefins. These unsaturated polymers are particularly suitable forfurther functionalization reactions. Examples of such functionalizationreactants includes alkylation with aromatic compounds, such as benzene,toluene, xylene, naphthalene, anisole, phenol or alkylphenols. The PAO'scan also react with maleic anhydride to give PAO-succinic anhydride,which can be further converted with amines or alcohols to correspondingsuccinimide or succinate esters. These imides and esters are superiordispersants.

The functionalized PAO can in turn be derivatized with a derivatizingcompound. (For purposes of this disclosure and the claims thereto theterm functionalized PAO encompasses derivatized PAO.) The derivatizingcompound can react with the functional groups of the functionalized PAOby means such as nucleophilic substitution, Mannich Base condensation,and the like. The derivatizing compound can be polar and/or containreactive derivative groups. Preferred derivatizing compounds areselected from hydroxy containing compounds, amines, metal salts,anhydride containing compounds and acetyl halide containing compounds.The derivatizing compounds can comprise at least one nucleophilic groupand preferably at least two nucleophilic groups. A typical derivatizedPAO is made by contacting a functionalized PAO, i.e., substituted with acarboxylic acid/anhydride or ester, with a nucleophilic reagent, e.g.,amine, alcohol, including polyols, amino alcohols, reactive metalcompounds and the like. (For more information please see U.S. Pat. No.6,022,929 column 33, line 27 to column 74, line 63.) Alternately aderivatized PAO may be made by contacting a functionalized PAO,substituted with a carboxylic acid/anhydride or ester, with anucleophilic reagent, e.g., amine, to make a quaternary ammoniumcompound or amine oxide.

The functionalized PAO's and/or derivatized PAO's have uses aslubricating additives which can act as dispersants, viscosity indeximprovers, or multifunctional viscosity index improvers. Additionallythey may be used as disinfectants (functionalized amines) and or wettingagents.

The functionalized PAO prepared herein may be used in oil additivation,lubricants, fuels and many other applications. Preferred uses includeadditives for lubricants and or fuels.

In particular embodiments herein, the PAO's disclosed herein, orfunctionalized/derivatized analogs thereof, are useful as additivesand/or base stocks, preferably in a lubricant.

The functionalized PAO's and/or derivatized PAO's produced herein haveuses as lubricating additives which can act as dispersants, viscosityindex improvers, or multifunctional viscosity index improvers.Additionally they may be used as disinfectants (functionalized amines)and or wetting agents.

Functionalized PAOs and/or derivatized PAOs having uses as dispersantstypically have an Mn of less than 1,000 g/mol, preferably less than 500g/mol, preferably less than 300 g/mol, and typically can range from 100g/mol to 500 g/mol, preferably from 200 g/mol to 400 g/mol, preferablyfrom 200 g/mol to 300 g/mol.

The functionalized PAOs and/or derivatized PAOs described herein havingMn's (g/mol) of greater than 100 g/mol, preferably 200 to 400 g/mol(preferably 200 to 300 g/mol) are useful for viscosity index improversfor lubricating oil compositions, adhesive additives, antifogging andwetting agents, ink and paint adhesion promoters, coatings, tackifiersand sealants, and the like. In addition, such PAOs may be functionalizedand derivatized to make multifunctional viscosity index improvers whichalso possess dispersant properties. (For more information please seeU.S. Pat. No. 6,022,929.)

The functionalized PAOs and/or derivatized PAOs described herein may becombined with other additives (such as viscosity index improvers,corrosion inhibitor, oxidation inhibitor, dispersant, lube oil flowimprover, detergents, demulsifiers, rust inhibitors, pour pointdepressant, anti-foaming agents, antiwear agents, seal swellant,friction modifiers, and the like (described for example in U.S. Pat. No.6,022,929 at columns 60, line 42-column 78, line 54 and the referencescited therein) to form compositions for many applications, including butnot limited to lube oil additive packages, lube oils, and the like.

Compositions containing these additives are typically blended into abase oil in amounts which are effective to provide their normalattendant function. Representative effective amounts of such additivesare illustrated as follows:

(Typical) (Preferred) Compositions wt %* wt %* Viscosity Index Improver   1-12  1-4 Corrosion Inhibitor 0.01-3 0.01-1.5 Oxidation Inhibitor0.01-5 0.01-1.5 Dispersant  0.1-10 0.1-5  Lube Oil Flow Improver 0.01-20.01-1.5 Detergents and Rust inhibitors 0.01-6 0.01-3   Pour PointDepressant   0.01-1.5 0.01-1.5 Anti-Foaming Agents  0.001-0.1 0.001-0.01Antiwear Agents 0.001-5  0.001-1.5  Seal Swellant  0.1-8 0.1-4  FrictionModifiers 0.01-3 0.01-1.5 Lubricating Base Oil Balance Balance *Wt %'sare based on active ingredient content of the additive, and/or upon thetotal weight of any additive-package, or formulation which will be thesum of the A.I. weight of each additive plus the weight of total oil ordiluent.

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the subject additives of this disclosure (inconcentrate amounts hereinabove described), together with one or more ofsaid other additives (said concentrate when constituting an additivemixture being referred to herein as an additive-package) whereby severaladditives can be added simultaneously to the base oil to form thelubricating oil composition. Dissolution of the additive concentrateinto the lubricating oil may be facilitated by solvents and by mixingaccompanied with mild heating, but this is not essential. The subjectfunctionalized or derivatized PAOs of the present disclosure can beadded to small amounts of base oil or other compatible solvents alongwith other desirable additives to form additive-packages containingactive ingredients in collective amounts of typically from about 2.5 toabout 90%, and preferably from about 15 to about 75%, and mostpreferably from about 25 to about 60% by weight additives in theappropriate proportions with the remainder being base oil.

The final formulations may employ typically about 10 wt % of theadditive-package with the remainder being base oil.

In another embodiment, the PAO's described herein can be use in anyprocess, blend or product disclosed in WO 2009/155472 or U.S. Pat. No.6,022,929, which are incorporated by reference herein.

In a preferred embodiment, this disclosure relates to a fuel comprisingany PAO produced herein. In a preferred embodiment, this disclosurerelates to a lubricant comprising any PAO produced herein.

Hydrogenation

Any of polyalphaolefins produced herein can be hydrogenated. Inparticular the polyalpha-olefin is preferably treated to reduceheteroatom containing compounds to less than 600 ppm, and then contactedwith hydrogen and a hydrogenation catalyst to produce a polyalpha-olefinhaving a bromine number less than 1.8. In a preferred embodiment, thetreated polyalpha-olefin comprises 100 ppm of heteroatom containingcompounds or less, preferably 10 ppm of heteroatom containing compoundsor less. (A heteroatom containing compound is a compound containing atleast one atom other than carbon and hydrogen.) Preferably thehydrogenation catalyst is selected from the group consisting ofsupported Group 7, 8, 9, and 10 metals, preferably the hydrogenationcatalyst selected from the group consisting of one or more of Ni, Pd,Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, supported on silica, alumina,clay, titania, zirconia, or mixed metal oxide supports. A preferredhydrogenation catalyst is nickel supported on keiselguhr, or platinum orpalladium supported on alumina, or cobalt-molydenum supported onalumina. Usually, a high nickel content catalyst, such as 60% Ni onkeiselguhr catalyst is used, or a supported catalyst with high amount ofCo—Mo loading. Alternately, the hydrogenation catalyst is nickelsupported on keiselguhr, silica, alumina, clay or silica-alumina.

A polyalpha-olefin is contacted with hydrogen and a hydrogenationcatalyst at a temperature from 25 to 350° C., preferably 100 to 300° C.In another preferred embodiment the polyalpha-olefin is contacted withhydrogen and a hydrogenation catalyst for a time period from 5 minutesto 100 hours, preferably from 5 minutes to 24 hours. In anotherpreferred embodiment the polyalpha-olefin is contacted with hydrogen anda hydrogenation catalyst at a hydrogen pressure of from 25 psi to 2500psi, preferably from 100 to 2000 psi. For further information onhydrogenation of PAO's please see U.S. Pat. No. 5,573,657 and “LubricantBase Oil Hydrogen Refining Processes” (page 119 to 152 of Lubricant BaseOil and Wax Processing, by Avilino Sequeira, Jr., Marcel Dekker, Inc.,NY, 1994.

This hydrogenation process can be accomplished in a slurry reactor in abatch operation or in a continuous stirred tank reactor (CSTR), wherethe catalyst in 0.001 wt % to 20 wt % of the PAO feed or preferably 0.01to 10 wt %, hydrogen and the polyalpha-olefins are continuously added tothe reactor to allow for certain residence time, usually 5 minutes to 10hours to allow complete hydrogenation of the unsaturated olefins and toallow proper conversion of the mm diads. The amount of catalyst added isusually very small just to compensate for the catalyst deactivation. Thecatalyst and hydrogenated PAO are continuously withdrawn from thereactor. The product mixture was then filtered, centrifuged or settledto remove the solid hydrogenation catalyst. The catalyst can beregenerated and reused. The hydrogenated PAO can be used as is orfurther distilled or fractionated to the right component if necessary.In some cases, when the hydrogenation catalyst show no catalystdeactivation over long term operation, the stir tank hydrogenationprocess can be carried out in a manner where a fixed amount of catalystis maintained in the reactor, usually 0.1 wt % to 10% of the totalreactant, and only hydrogen and PAO feed are continuously added atcertain feed rate and only hydrogenated PAO was withdrawn from thereactor.

The hydrogenation process can also be accomplished by a fixed bedprocess, in which the solid catalyst is packed inside a tubular reactorand heated to reactor temperature. Hydrogen and PAO feed can be fedthrough the reactor simultaneously from the top or bottom orcounter-currently to maximize the contact between hydrogen, PAO andcatalyst and to allow best heat management. The feed rate of the PAO andhydrogen are adjusted to give proper residence to allow completehydrogenation of the unsaturated olefins in the feed and to allowdesirable conversion of mm triads in the process. The hydrogenated PAOfluid can be used as is or further distilled or fractionated to give theright component, if necessary. Usually, the finished hydrocarbon PAOfluids have bromine number less than 2 and have reduced amount of mmtriads than the unhydrogenated PAO.

III. Apparatus for Producing PAOs

The present disclosure also includes apparatus for producing a hybridtrimer from a PAO dimer. In conventional processes and apparatus toproduce hybrid trimers, and after generation of the PAO dimer in a firstoligomerization reactor, the PAO dimer starting material can be enrichedby removing impurities for feed into a second oligomerization reactor.This process, however, involves an additional separation operationbecause feeding the trimer and higher (tetramer+) oligomers to thesecond oligomerization reactor produces an undesired heavier productfrom the second oligomerization reaction. Being able to eliminate theseparation equipment between these two reactors can dramatically reducecapital spending and simplify plant design and operation.

In an example, the process eliminates the need for a separation stagebetween a first oligomerization operation and a second oligomerizationoperation. The inventors have found that the desired hybrid trimerproduced from the process, which includes a first and secondoligomerization, meets and/or exceeds conventional process yields ofhybrid trimer, even while removing the separation operation between thetwo oligomerizations. The inventors have found that by using themetallocene dimer selective catalyst, the olefin distribution producedin the first oligomerization reactor (e.g., the metallocene reactor)contains significant amounts of dimer and very small amounts of trimerand higher oligomers (tetramer+). With that distribution, the inventorshave also found that an apparatus for producing hybrid trimers can bedesigned without separation equipment disposed between the firstoligomerization reactor and the second oligomerization reactor (e.g.,separation equipment is merely optional) because there is no longer arequirement to separate out the higher molecules. Therefore, theprocesses and configurations described herein can greatly simplify PAOprocessing while maintaining high yields of desired PAO products, suchas low viscosity PAO trimers or “hybrid trimers”.

Conventional apparatus and processes for the production of low viscosityPAO using conventional metallocene technology is shown in FIG. 1. Asshown in FIG. 1, the conventional apparatus and processes requires amonomer/dimer separation operation after forming the PAO dimer in thefirst oligomerization reactor.

With reference to FIG. 1, the conventional apparatus includes a feedline 102 (LAO feed 1) for directing alpha-olefin monomer into a firstoligomerization reactor 104 to form a first oligomerization reactoreffluent. The first oligomerization reactor effluent of line 106 istransferred to a separation stage 108 (e.g., a first distillation unit)to remove PAO trimers, tetramers, and higher oligomers (tetramer+) fromthe first oligomerization reactor effluent. Separation stage 108 caninclude a pre-heater, distillation column, vacuum system, overheadcondenser, overhead accumulator, reflux pump, reboiler, and/or bottomspump. The monomer/dimer is removed as a first tops fraction via a line110 and is then transferred to a second oligomerization reactor 116where it can combine with another alpha-olefin monomer of line 114 (LAOfeed 2) and form a second oligomerization reactor effluent. A firstbottoms fraction of line 112 can also be separated. The secondoligomerization reactor effluent flows to a second distillation unit 120via line 118 where byproducts and/or contaminants can be separated fromthe second reactor effluent. The byproducts and/or contaminants may beremoved as a second tops fraction via a line 122 and recycled back tosecond reactor 116 or purged from the process via line 124. The secondbottoms fraction, including PAO dimer, trimer, tetramer, and higheroligomers, is then transferred to a hydrogenation unit 128 via line 126.The first bottoms fraction in line 112 (containing, e.g., PAO trimer,tetramer and heavier oligomers) can also combine with second bottomsfraction and flow into the hydrogenation unit 128. The hydrogenationeffluent can be transferred, via line 130, to the third distillationunit 132 where PAO dimer is separated from the other components of thehydrogenation effluent such as trimers, tetramers, and higher oligomers.The dimers are removed as a third tops fraction from the third reactoreffluent via a line 134. The bottoms fraction from the thirddistillation unit 132 is transferred to a fourth distillation unit 138via a line 136, where PAO trimer is partially separated from othercomponents of the third distillation effluent. The PAO trimer can beremoved as a third tops fraction from the fourth distillation unit 138via line 140, and a fourth distillation effluent that includes trimers,tetramers, and higher oligomers can be removed from the fourthdistillation unit 138 via line 142.

The conventional metallocene technology used in the conventionalapparatus involves a separation stage between the first oligomerizationand second oligomerization. As discussed below, the separation stage canbe eliminated without reducing the yield of desired PAO trimer, ascompared to conventional apparatus.

FIG. 2 is a diagram illustrating an apparatus for carrying out certainaspects of the present disclosure according to at least one embodiment.More generally, a configuration shown in FIG. 2 or similar to FIG. 2 canbe used for forming poly alpha-olefins of the present disclosure. FIG. 2is a non-limiting example of a configuration.

As shown in FIG. 2, an apparatus can include a feed line 202 (LAO feed1) coupled with a first reactor 204 (e.g., an oligomerization reactor).During use, a feed of the feed line 202 can include an alpha-olefin. Thefirst reactor 204 can be coupled (e.g., directly) with a second reactor208 (e.g., an oligomerization reactor) via a line 206. A first reactoreffluent (e.g., intermediate PAO) of the line 206 can be transferred tothe second reactor 208 where the first reactor effluent can undergo asecond oligomerization, by, e.g., a BF₃-mediated process, to form asecond reactor effluent. The second reactor 208 can be coupled to afirst distillation unit 212 via a line 210. The second reactor effluent(including the hybrid trimer) can be transferred to the firstdistillation unit 212 where byproducts and/or contaminants, such asmonomer and catalyst components can be separated from the second reactoreffluent. The byproducts and/or contaminants may be removed as a firsttops fraction via a line 214 and recycled back to second reactor 208 orpurged from the process via line 216. The first distillation unit 212can be further coupled to a third reactor (e.g., a hydrogenation unit)220. The first distillation effluent (including PAO trimer) of a line218 can be transferred to the hydrogenation unit 220. The firstdistillation effluent may further include dimers, tetramers and higheroligomers (if any). The hydrogenation unit 220 can be coupled to asecond distillation unit 224 via a line 222. The hydrogenation effluentcan be transferred to the second distillation unit 224 where PAO dimercan be separated from the other components of the hydrogenation effluentsuch as trimers, tetramers, and higher oligomers (if any). The dimersmay be removed as a second tops fraction from the hydrogenation effluentvia a line 226. Optionally, the second distillation unit 224 can befurther coupled to a third distillation unit 230 via a line 228. Asecond distillation effluent that includes trimers, tetramer, and higheroligomers (if any) can be transferred to the third distillation unit 230where PAO trimer can be partially separated from other components of thesecond distillation effluent. The PAO trimer can be removed as a thirdtops fraction from the third distillation unit 230 via line 232, and athird distillation effluent (e.g., a low viscosity PAO effluent) thatincludes trimers, tetramers, and higher oligomers (if any) can beremoved from the third distillation unit 230 via line 234.

In at least one embodiment, the line 206 can be free of a separationstage, e.g., any suitable separation device such as one that separates alighter component from a heavier component, such as a flash drum(s),multiple flash stages in series, atmospheric distillation column(s),vacuum distillation column(s), stripper(s), steam stripper(s), nitrogenstripper(s), membrane separation(s), chromatography column(s), and/orcrystallization(s).

In some embodiments, one or more additional apparatus components aredisposed between the first reactor and the second reactor. For example,one or more heat exchangers or mixers is disposed between the firstreactor and the second reactor.

In at least one embodiment, the third tops fraction or a portion of thethird tops fraction can have a KV (100° C.) of 4 cSt or less, such asless than about 3.6 cSt.

In at least one embodiment, the third tops fraction or a portion of thethird tops fraction has a KV (100° C.) between 3.4 and 4.0 and a Noackvolatility (y) that does not exceed the value defined by the followingequation, where x is the kinematic viscosity at 100° C.:y=−21.0x ²+148.7x−248.9

In at least one embodiment, the third distillation effluent or a portionof the third distillation effluent can have a KV (100° C.) of from about4 cSt to about 10 cSt, such as from about 5 cSt to about 7 cSt.

In at least one embodiment, the third distillation is performed suchthat at the bottoms stream consists of at least 5 wt % trimer, such asfrom 5 wt % trimer to 40 wt % trimer, such as from 10 wt % trimer to 30wt % trimer, such as from 15 wt % trimer to 25 wt % trimer.

In at least one embodiment, the first oligomerization can utilize themetallocene dimer catalysts and the metallocene dimer selectiveprocesses discussed in Section I, and the first oligomerization can formthe products discussed in Section I. In at least one embodiment, thesecond oligomerization can utilize the catalysts and processes forproducing PAO trimers (hybrid trimers) discussed in Section II, and canform the products discussed in Section II.

IV. The First Oligomerization Reaction

In some embodiments according to the present disclosure, a process formaking a poly alpha-olefin can include contacting a feed containing aC₆-C₃₂ alpha-olefin and optional ethylene with a catalyst systemcomprising a metallocene compound in a polymerization reactor underpolymerization conditions to effect a polymerization reaction to obtaina product, wherein the metallocene compound is represented by formula(MC-I), wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², M, X, and m can be as described above.

In some embodiments, the metallocene compound is represented by formula(MC-II), wherein each of R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, M, X, m, can be as described above.

In some embodiments of the process, the polymerization reaction exhibitsa selectivity toward a combination of greater than or equal to about96.5 mol % vinylidenes, from 0.5 mol % to 3.5 mol % trisubstitutedvinylenes, less than or equal to about 1.5 mol % disubstitutedvinylenes, and less than or equal to about 1.5 mol % vinyls, based ontotal moles of vinyls, vinylidenes, disubstituted vinylenes, andtrisubstituted vinylenes in the first reactor effluent.

In some embodiments of the process, the polymerization reaction exhibitsa selectivity toward a combination of vinylidenes of equal to or greaterthan 97.0 mol %, such as equal to or greater than 97.9 mol %;trisubstituted vinylenes of less than 2.1 mol %; disubstituted vinylenesof 0.5 mol % or less; and vinyls of 1.0 mol % or less, based on totalmoles of vinyls, vinylidenes, disubstituted vinylenes, andtrisubstituted vinylenes in the first reactor effluent. In someembodiments of the process, the polymerization reaction exhibits aselectivity towards a combination of vinylidenes and trisubstitutedvinylenes of collectively greater than 98.0 mol %, such as greater than98.5 mol %, and a combination of disubstituted vinylenes and vinyls ofcollectively less than 2.0 mol %, such as less than 1.5 mol %, based ontotal moles of vinyls, vinylidenes, disubstituted vinylenes, andtrisubstituted vinylenes in the first reactor effluent.

In some embodiments of the process the polymerization reaction resultsin the first reactor effluent having a number average molecular weight(M_(n)) of 1500 g/mol or less, such as from 300 to 800 g/mol, asmeasured by ¹H NMR. In some embodiments, the catalyst system furthercomprises a non-coordinating anion type activator, such as wherein thenon-coordinating anion type activator comprises: dimethylaniliniumtetrakisperfluorophenylborate, dimethylaniliniumtetrakisperfluoronaphthylborate, triphenylcarboniumtetrakisperfluorophenylborate, triphenylcarboniumtetrakisperfluoronaphthylborate, dimethylaniliniumtetrakisperfluorophenylaluminate, dimethylaniliniumtetrakisperfluoronaphthylaluminate, or a combination thereof.

In some embodiments of the process, the polymerization conditionscomprise a reaction temperature from 40° C. to 150° C.; an averageactivity level of at least 1200 g/s·mol; the product exhibits anoligomer yield of at least 10%; or a combination thereof.

In some embodiments of the process, the feed comprises C₆-C₂₄alpha-olefin; and any combination of C₂-C₅ alpha-olefins arecollectively present in the alpha-olefin feed at no higher than 25 mol%, based on the total moles of the alpha-olefins supplied to thepolymerization reactor, such as wherein the alpha-olefin feed issubstantially free of ethylene, propylene, C₄ alpha-olefins, and C₅alpha-olefins; or a combination thereof. In some embodiments, thealpha-olefin feed is substantially free (or absent, 0 mol %) ofpropylene, C₄ alpha-olefins, and C₅ alpha-olefins; or a combinationthereof and optionally comprises less than 25 mol % ethylene, such asless than 15 mol %, such as less than 5 mol %.

In embodiments of the present disclosure, an unsaturated polyalpha-olefin product comprises greater than or equal to about 80 mol %vinylidenes, such as 90 mol % vinylidenes, such as 96.5 mol %vinylidenes, based on total moles of vinyls, vinylidenes, disubstitutedvinylenes, and trisubstituted vinylenes contained therein. In someembodiments, the unsaturated poly alpha-olefin product comprises 96.5mol % to 99.9 mol % of vinylidenes; 0.1 mol % to 3.5 mol % oftrisubstituted vinylenes; 3.0 mol % or less of disubstituted vinylenes;3.0 mol % or less of vinyl groups; based on total moles of vinylidenes,trisubstituted vinylenes, disubstituted vinylenes, and vinylidenescontained therein; and a number average molecular weight (M_(n)) of 1500g/mol or less as measured by ¹H NMR.

In some embodiments, the unsaturated poly alpha-olefin product comprisesless than or equal to about 1.0 mol % disubstituted vinylenes, whenpresent; less than or equal to about 1.0 mol % vinyl groups whenpresent; and a number average molecular weight (Mn) of 1000 g/mol orless as measured by ¹H NMR.

In some embodiments, the unsaturated poly alpha-olefin product comprisesfrom 98 mol % to 99.5 mol % of a combination of vinylidenes andtrisubstituted vinylenes; 0.5 mol % to 2 mol % of a combination ofdisubstituted vinylenes and vinyl groups, and a number average molecularweight (Mn) of 800 g/mol or less as measured by ¹H NMR.

In embodiments of the present disclosure, a catalyst compound suitableto produce a first reactor effluent from C₆-C₃₂ alpha-olefin underpolymerization conditions comprises a polymerization selectivitysuitable to form a first reactor effluent comprising greater than orequal to about 80 mol % vinylidenes, such as 90 mol % vinylidenes, suchas 96.5 mol % vinylidenes, based on total moles of vinyls, vinylidenes,disubstituted vinylenes, and trisubstituted vinylenes in the firstreactor effluent.

In some embodiments, the catalyst compound comprises a polymerizationselectivity suitable to form a first reactor effluent comprising 96.5mol % to 99.9 mol % of vinylidenes; 0.1 mol % to 3.5 mol % oftrisubstituted vinylenes; 2.0 mol % or less of disubstituted vinylenes;2.0 mol % or less of vinyl groups; based on total moles of vinyls,vinylidenes, disubstituted vinylenes, and trisubstituted vinylenes inthe first reactor effluent; and a number average molecular weight (Mn)of 1500 g/mol or less as measured by ¹H NMR.

In some embodiments, the catalyst compound comprises a polymerizationselectivity suitable to form a first reactor effluent comprising:greater than or equal to about 96.5 mol % vinylidenes; less than orequal to about 3.5 mol % trisubstituted vinylenes; less than or equal toabout 1.0 mol % disubstituted vinylenes, when present; less than orequal to about 1.0 mol % vinyl groups when present; based on total molesof vinyls, vinylidenes, disubstituted vinylenes, and trisubstitutedvinylenes in the first reactor effluent; and a number average molecularweight (M_(n)) of 1500 g/mol or less as measured by ¹H NMR.

IV. A First Reactor Effluent

The first reactor effluent includes PAOs. PAOs are polymeric, typicallyoligomeric, molecules produced from the polymerization reactions ofalpha-olefin monomer molecules in the presence of a catalyst system. Anunsaturated poly alpha-olefin molecule in the material of the presentdisclosure contains a C═C bond therein. Each PAO molecule of the firstreactor effluent has a carbon chain with the largest number of carbonatoms, which is designated the carbon backbone of the molecule. Anynon-hydrogen group attached to the carbon backbone other than to thecarbon atoms at the very ends thereof is defined as a pendant group. Thenumber of carbon atoms in the longest carbon chain in each pendant groupis defined as the length of the pendant group. The backbone typicallycomprises the carbon atoms derived from the C═C bonds in the monomermolecules participating in the polymerization reactions, and additionalcarbon atoms from monomer molecules and/or molecules in the catalystsystem that form the two ends of the backbone. A typical PAO molecule ofthe first reactor effluent can be represented by the following formula(F-1):

where R¹, R^(2a), R^(2b), R³, each of R⁴ and R⁵, R⁶, and R⁷, the same ordifferent at each occurrence, independently represents a hydrogen or asubstituted or unsubstituted hydrocarbyl (such as an alkyl) group, and nis a non-negative integer corresponding to the degree of polymerization.Where R¹, R² and R^(2b) are all hydrogen, (F-1) represents a vinyl PAO;where R′ is not hydrogen, and both R^(2a) and R^(2b) are hydrogen, (F-1)represents a vinylidene PAO; where R′ is hydrogen, and only one ofR^(2a) and R^(2b) is hydrogen, (F-1) represents a disubstituted vinylenePAO; and where R¹ is not hydrogen, and only one of R^(2a) and R^(2b) ishydrogen, then (F-1) represents a trisubstituted vinylene PAO.

Where n=0, (F-1) represents a PAO dimer produced from the reaction oftwo monomer molecules after a single addition reaction between two C═Cbonds.

Where n=m, m being a positive integer, (F-1) represents a moleculeproduced from the reactions of m+2 monomer molecules after m+l steps oflinear addition reactions between two C═C bonds.

Thus, where n=1, (F-1) represents a trimer produced from the reactionsof three monomer molecules after two steps of linear addition reactionsbetween two C═C bonds.

Assuming a carbon chain starting from R¹ and ending with R⁷ has thelargest number of carbon atoms among all straight carbon chains existingin (F-1), that carbon chain starting from R′ and ending with R⁷ havingthe largest number of carbon atoms constitutes the carbon backbone ofthe first reactor effluent molecule (F-1). R², R³, each of R⁴ and R⁵,and R⁶, which can be substituted or unsubstituted hydrocarbyl (such asalkyl) groups, are pendant groups (if not hydrogen).

If only alpha-olefin monomers are used in the polymerization process,and no isomerization of the monomers and oligomers ever occurs in thereaction system during polymerization, about half, typically at leastone more than half, of R¹, R^(2a), R^(2b), R³, all R⁴ and R⁵, R⁶, and R⁷would be hydrogen, and one of R¹, R^(2a), R^(2b), R⁶, and R⁷ would be ahydrocarbyl, such as methyl, and about half, typically less than half,of groups R¹, R^(2a), R^(2b), R³, all R⁴ and R⁵, R⁶, and R⁷ would behydrocarbyl groups introduced from the alpha-olefin monomer molecules.In a specific example of such case, assuming R^(2a) and R^(2b) arehydrogen, R³, all R⁵, and R⁶ are hydrogen, and R¹, all R⁴, and R⁷ have 8carbon atoms in the longest carbon chains contained therein, and n=8,then the carbon backbone of the (F-1) PAO molecule would comprise 35carbon atoms, and the average pendant group length of the pendant groups(the initial ═CR^(2a)R^(2b) group, and all of R⁴) would be 7.22 (i.e.,(1+8*8)/9). Such an PAO molecule, which may be produced by polymerizing1-decene using certain metallocene catalyst systems, such as describedin greater detail below, can be represented by formula (F-2) below:

In such a molecule, the longest 5%, 10%, 20%, 40%, 500, and 100% of thependant groups have average pendant group length of Lpg(5%) of 8,Lpg(10%) of 8, Lpg(20%) of 8, Lpg(50%) of 8, and Lpg(100%) of 7.22,respectively.

Depending on the polymerization catalyst system used, however, differentdegrees of isomerization of the monomers and/or oligomers can occur inthe reaction system during the polymerization process, resulting indifferent degrees of substitution on the carbon backbone. In a specificexample of such case, assuming R^(2a) and R^(2b) are both hydrogen, R³and all R⁵ are methyl, R⁶ is hydrogen, R¹ has 8 carbon atoms in thelongest carbon chain contained therein, all R⁴ and R⁷ have 7 carbonatoms in the longest carbon chain contained therein, and n=8, then thecarbon backbone of the (F-1) PAO molecule would comprise 34 carbonatoms, and the average pendant group length of the pendant groups (theinitial ═CR^(2a)R^(2b) group, all R⁴, and R⁵) would be ˜3.7 (i.e.,(1+1+7*8+8*1)/18). Such a PAO molecule, which may be produced bypolymerizing either 1-decene, with a given level and pattern ofisomerization, or by polymerizing a combination of 1-decene and2-decene, using certain non-metallocene catalyst systems, such asdescribed in greater detail below, can be represented by the followingformula (F-3):

In this molecule, the longest 5%, 10%, 20%, 40%, 50%, and 100% of thependant groups have average pendant group lengths of Lpg(5%) of 7,Lpg(10%) of 7, Lpg(20%) of 7, Lpg(50% o) of 6.3, and Lpg(100%) of 3.7,respectively.

One skilled in the art, with knowledge of the molecular structure or themonomer(s) used in the polymerization step for making the first reactoreffluent, the process conditions (catalyst used, reaction conditions,etc.), and the polymerization reaction mechanism, inter alia, canapproximate the molecular structure of the PAO molecules, thus thependant groups attached to the carbon backbone, and hence approximatevalues of Lpg(5%), Lpg(10%), Lpg(20), Lpg(50%), and Lpg(00%),respectively.

One skilled in the art can determine the Lpg(5%), Lpg(10%), Lpg(20%),Lpg(50%), and Lpg(100%) values of a given first reactor effluent byusing separation and characterization techniques available to polymerchemists. For example, gas chromatography/mass spectroscopy machinesequipped with boiling point column separator can be used to separate andidentify individual chemical species and fractions; and standardcharacterization methods such as NMR, IR, and UV spectroscopy can beused to further confirm the structures.

The first reactor effluent of the present disclosure may be ahomopolymer made from a single alpha-olefin monomer or a copolymer madefrom a combination of two or more alpha-olefin monomers. In someembodiments, the alpha-olefin monomer(s) can include, consistessentially of, or be 1-hexene, 1-octene, 1-decene, 1-dodecene, or acombination thereof, such as 1-octene, 1-decene, and 1-dodecene.

The first reactor effluent of the present disclosure may be produced byusing a catalyst system comprising a specific type of metallocenecompound, such as described in detail below. The first reactor effluentcan be substantially free of the alpha-olefin monomer(s), and mayadvantageously contain vinylidenes at a high concentration, such as inthe range from c1 to c2 mol % in total, where c1 and c2 can be,independently, about 80, about 85, about 90, about 91, about 92, about93, about 94, about 95, about 96, about 96.5, about 97, about 98, about99, about 99.5, or about 99.9, based on the total moles of vinyls,vinylidenes, disubstituted vinylenes, and trisubstituted vinylenes, aslong as c1<c2. In some embodiments, c1=90 and c2=99; c1=91 and c2=99;c1-92 and c2=98; c1=93 and c2=97; c1=96.5 and c2=99.9; or c1-98 andc2=99.5. Without intending to be bound by a particular theory, it isbelieved that the high concentrations of vinylidenes can be achievedpartly by the unique structure of the metallocene compound used in thecatalyst system.

Between the vinylidenes and trisubstituted vinylenes in the firstreactor effluent of the present disclosure, trisubstituted vinylenestend to have a considerably lower concentration than the vinylidenes. Insome embodiments, the first reactor effluent of the present disclosurecan contain a concentration of trisubstituted vinylenes in the rangefrom c3 to c4 mol %, based on the total moles of the vinyls,vinylidenes, disubstituted vinylenes, and trisubstituted vinylenes,where c3 and c4 can be, independently, about 0, about 0.1, about 0.5,about 1.0, about 1.5, about 2.0, about 2.5, about 3.0, about 3.5, about4.0, about 4.5, about 5.0, about 5.5 or about 6.0, as long as c3<c4. Insome embodiments, c3=0.5 and c4=5.5; c3=1.0 and c4=5.0; c3=0.5 andc4=4.0; c3=0 and c4=4.0; c3=0.1 and c4=3.5; or c3=0.5 and c4=2.

In some embodiments, the first reactor effluent of the presentdisclosure can contain a high combined concentration of vinylidenes andtrisubstituted vinylenes, the combined concentration being in the rangefrom c5 to c6 mol %, based on the total moles of the vinyls,vinylidenes, disubstituted vinylenes, and trisubstituted vinylenes,where c5 and c6 can be, independently, about 85, about 90, about 91,about 92, about 93, about 94, about 95, about 96, about 97, about 98,about 99, or about 99.5, based on the total moles of vinyls,vinylidenes, disubstituted vinylenes, and trisubstituted vinylenes, aslong as c5<c6. In some embodiments, c5=90 and c6-99.5; c5=92 andc6=99.5; c5=94 and c6-99; c5=95 and c6-99; or c5=98 and c6-99.5.

The first reactor effluent of the present disclosure can containdisubstituted vinylenes at a low concentration in the range from c7 toc8 mol %, based on the total moles of vinyls, vinylidenes, disubstitutedvinylenes, and trisubstituted vinylenes, where c7 and c8 can be about 0,about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about0.7, about 0.8, about 1.0, about 1.2, about 1.4, about 1.6, about 1.8,about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, orabout 5.0, as long as c7<c8. In some embodiments, c7=0 and c8=4.0; c7=0and c8=3.0; c7=0 and c8=2.0; c7=0 and c8=1; c7=0 and c8=1.2; or c7=0.1and c8=2.5. Without intending to be bound by a particular theory, it isbelieved that such low concentrations of disubstituted vinylenes in thefirst reactor effluent are achieved by the low selectivity toward theseolefins in the polymerization reactions, which can be provided at leastpartially by the unique structure of the metallocene compound in thecatalyst system used in the polymerization reaction.

Depending on the metallocene compound used in the catalyst system, thefirst reactor effluent of the present disclosure can contain vinyls at alow concentration, e.g., from c9 to c10 mol %, based on the total molesof vinyls, vinylidenes, disubstituted vinylenes, and trisubstitutedvinylenes, where c9 and c10 can be about 0, about 0.1, about 0.2, about0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 1.0,about 1.2, about 1.4, about 1.6, about 1.8, about 2.0, about 2.5, about3.0, about 3.5, about 4.0, about 4.5, or about 5.0, as long as c9<c10.In some embodiments, c9=0 and c10=4.0; c9=0 and c10=3.0; c9=0 and c10=2;c9=0 and c10=1.6; c9=0 and c10=1.0; or c9=0.1 and c10=1.2. Withoutintending to be bound by a particular theory, it is believed that suchlow concentration of vinyls in the first reactor effluent are achievedby the low selectivity toward vinyls in the polymerization reactions,which can be provided by choosing the molecular structure of themetallocene compound in the catalyst system used in the polymerizationreaction.

In some embodiments, the first reactor effluent of the presentdisclosure can contain a low combined concentration of vinyls anddisubstituted vinylenes, the combined concentration being in the rangefrom c11 to c12 mol %, based on the total moles of the vinyls,vinylidenes, disubstituted vinylenes, and trisubstituted vinylenes,where c11 and c12 can be, independently, about 0, about 0.1, about 0.2,about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about1.0, about 1.2, about 1.4, about 1.6, about 1.8, about 2.0, about 2.5,about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, or6.0, as long as c11<c12. In some embodiments, c11=0 and c12=5.0; c11=0and c12=4.0; c11=0.5 and c12=2; c11=0.5 and c12=4.5; or c11=0.8 andc12=5.0.

Thus, the first reactor effluent of the present disclosure can typicallycomprise a plurality of PAO molecules, which may be the same ordifferent. Each PAO molecule of the first reactor effluent can comprisea plurality of pendant groups, which may be the same or different, andthe longest about 5%, about 10%, about 20%, about 40% a, about 50%, andabout 100% of the pendant groups of all of the olefin molecules of thefirst reactor effluent have an average pendent group length of Lpg(5%),Lpg(10%), Lpg(20%), Lpg(40%), Lpg(50%), and Lpg(100%), respectively. Insome embodiments, at least one of the following conditions are met:

-   -   (i) a1≤Lpg(5%)≤a2, where a1 and a2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0 15.5,        or 16.0, as long as a1<a2;    -   (ii) b1≤Lpg(10%)≤b2, where b1 and b2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0,        as long as b1<b2;    -   (iii) c1≤Lpg(20%)≤c2, where c1 and c2 can be, independently,        4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5,        10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or        15.0, as long as c1<c2;    -   (iv) d1≤Lpg(40%)≤d2; where d1 and d2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0,        as long as d1<d2;    -   (v) e1≤Lpg (50%)≤e2; where e1 and e2 can be, independently, 4.0,        4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0,        10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, or 14.0, as long as        e1<e2; and    -   (vi) f1≤Lpg(100%)≤f2, where f1 and f2 can be, independently,        4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5,        10.0, 10.5, 11.0, 11.5, 12.0, 12.5, or 13.0, as long as f1<f2.

In some embodiments, at least about 60% o of the pendent groups onolefin molecules in the first reactor effluent are straight chain alkylshaving at least 4 (e.g., at least 6, at least 8, or at least 10) carbonatoms. In some embodiments, at least 90% of the pendent groups on theolefin molecules in the first reactor effluent are straight chain alkylshaving at least 4 (e.g., at least 6, at least 8, or at least 10) carbonatoms.

The first reactor effluent of the present disclosure may have variouslevels of regio-regularity. For example, each PAO molecule of the firstreactor effluent may be substantially atactic, isotactic, orsyndiotactic. A category of metallocene compounds can lack C₁, C₂, andC_(s) symmetry. Without intending to be bound by a particular theory, itis believed that PAO materials made by using such asymmetricalmetallocene-based catalyst system can tend to be atactic.

The first reactor effluent of the present disclosure can have viscosityvarying in a broad range. For example, the first reactor effluent mayhave a KV100 in a range from about 1 to about 5000 cSt, such as about 1to about 3000 cSt, about 2 to about 2000 cSt, about 2 to about 1000 cSt,about 2 to about 800 cSt, about 2 to about 600 cSt, about 2 to about 500cSt, about 2 to about 400 cSt, about 2 to about 300 cSt, about 2 toabout 200 cSt, or about 5 to about 100 cSt. The exact viscosity of thefirst reactor effluent can be controlled by, e.g., monomer used,polymerization temperature, polymerization reactor residence time,catalyst used, concentration of catalyst used, distillation andseparation conditions, and mixing multiple first reactor effluent withdifferent viscosity.

In addition, the first reactor effluent of the present disclosureadvantageously have a low polydispersity index (PDI) in the range fromabout 1.0 to about 5.0 (e.g., from about 1.2 to about 4.0, from about1.3 to about 3.0, from about 1.4 to about 2.5, from about 1.5 to about2.0, or from about 1.6 to about 1.8). A narrow molecular weightdistribution of the PAO molecules of the first reactor effluent can beachieved by using metallocene-compound-based catalyst systems in thepolymerization step under controlled polymerization conditions(temperature fluctuation, residence time, and the like). Such narrow PDIcan be desirable in that it defines a material with a high degree ofhomogeneity in molecular weight, molecular size, rheology behavior,viscosity index, and degrading behavior (such as shear stability andoxidation stability).

In general, the product in the first reactor effluent of the presentdisclosure can have an average molecular weight that can vary widely(and correspondingly, a KV100 that can vary widely). In someembodiments, the product of the first reactor effluent can have a numberaverage molecular weight of Mn, where Mn1≤Mn≤Mn2, where Mn1 and Mn2 canbe, independently, about 150, about 200, about 300, about 400, about500, about 600, about 700, about 800, about 900, about 1000, about 1100,about 1200, about 1300, about 1400, about 1500, about 1700, about 2000,about 2500, about 3000, about 3500, about 4000, about 4500, about 5000,about 6000, about 7000, about 8,000, about 9000, or about 10000 g/mol,as long as Mn1<Mn2. In some embodiments, the product of the firstreactor effluent can have a number average molecular weight of about3000 g/mol or less, e.g., about 2500 g/mol or less, about 2000 g/mol orless, about 1700 g/mol or less, about 1500 g/mol or less, about 1400g/mol or less, about 1300 g/mol or less, about 1200 g/mol or less, about1100 g/mol or less, about 1000 g/mol or less, about 900 g/mol or less,about 800 g/mol or less, about 700 g/mol or less, about 650 g/mol orless, about 620 g/mol or less, about 600 g/mol or less, about 520 g/molor less, about 500 g/mol or less, about 400 g/mol or less, about 380g/mol or less, about 370 g/mol or less, about 360 g/mol or less, about350 g/mol or less, about 340 g/mol or less, about 330 g/mol or less, orabout 320 g/mol or less; typically, as the product can exclude olefinmonomers but may include dimers and higher mers, the number averagemolecular weight can optionally be at least about 100 g/mol, e.g., atleast about 150 g/mol or at least about 200 g/mol, depending upon themolecular weight of a monomeric feed olefin component.

In general, it can be desired that the first reactor effluent of thepresent disclosure has a bromine number in a range from Nb(PAO)1 toNb(PAO)2, where Nb(PAO)1 and Nb(PAO)2 can be, independently, 1.0, 1.5,2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, or even 10.0,15.0, 10.0, as long as Nb(PAO)1<Nb(PAO)2. In some embodiments, a greatmajority, such as at least about 80, about 85, about 90, about 95, about98, or even about 99 mol % of the molecules in the first reactoreffluent of the present disclosure may be unsaturated.

Because of the presence of the C═C bonds in the PAO molecules in thefirst reactor effluent, when exposed to O₂ molecules (such as whenexposed to air), the first reactor effluent can be oxidized if notprotected by a more reactive material toward O₂. To that end, in thefirst reactor effluent, anti-oxidant materials may be added to prolongshelf life and facilitate handling, storage, and transportation thereof.Non-limiting examples of such anti-oxidants and the use quantity thereofare given in paragraphs [0101]-[0108], pages 9 and 10 of U.S. PatentPublication No. 2010/0087349, the content of which is herebyincorporated by reference in its entirety.

IV. B. The Catalyst System of the First Oligomerization

In embodiments, the catalyst system of the first oligomerizationcomprises a catalyst compound, such as a metallocene compound which isactivated by one or more activators. The catalyst system may furtherinclude a solvent, a support, one or more scavengers, accelerators,and/or the like.

IV. B.1 The Metallocene Compound of the First Oligomerization

The initial part to a catalyst system of the first oligomerizationdescribed herein is a metallocene compound.

The metallocene compound used in the process of the present disclosurefor making PAOs is generally represented by formula (Z) or (Z-1):

wherein:

-   -   each R¹, R², and R³ is, independently, hydrogen or a substituted        or unsubstituted linear, branched (such as branched linear), or        cyclic C₁ to C₂₀, preferably C₁-C₈, hydrocarbyl group, wherein        one of R¹, R², and R³ is a substituted or unsubstituted linear,        branched (such as branched linear), or cyclic C₁ to C₂₀,        preferably C₁-C₈, hydrocarbyl group, and either (i) two of R¹,        R², and R³ are each a hydrogen, or (ii) one of R¹, R², and R³ is        a hydrogen or a substituted or unsubstituted linear, branched        (such as branched linear), or cyclic C₁ to C₂₀, preferably        C₁-C₈, hydrocarbyl group, and one of R¹, R², and R³, taken        together with R¹⁶, is a bridging group connecting the first and        second cyclopentadienyl rings;

R⁴ and R⁵ are each independently a substituted or unsubstituted linear,branched (such as branched linear), or cyclic C₁-C₃₀ hydrocarbyl group,or R⁴ and R⁵, taken together with the carbon atoms in the firstcyclopentadienyl ring to which they are directly connected, collectivelyform one or more substituted or unsubstituted rings annelated to thefirst cyclopentadienyl ring;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched (such as branched linear),or cyclic C₁ to C₂₀, preferably C₁-C₈, hydrocarbyl group;

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branched (suchas branched linear), or cyclic C₁ to C₂₀, preferably C₁-C₈, hydrocarbylgroup, a substituted silyl group, or a substituted germanyl group, or,taken together with one of R¹, R², and R³, is a bridging groupconnecting the first and second cyclopentadienyl rings, preferably atleast three (preferably at least four, preferably all five) of R¹², R¹³,R¹⁴, R¹⁵, and R¹⁶ are not hydrogen, optionally two or more of R¹², R¹¹,R¹⁴, R¹⁵ and R¹⁶ moieties may together form a fused ring or ring system,provided that the fused ring or ring system is not unsaturated when R¹is bridged to R¹⁶, and provided that R² is not Me when R¹ or R³ isbridged to R¹⁶;

M is a transition metal (preferably a group 4 transition metal,preferably Hf, Ti, or Zr), having an integer valency of v, preferably vis 3, 4, or 5;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system;

-   -   m is an integer equal to v-2 (preferably m is 1, 2 or 3,        preferably 2), preferably M is Zr or Hf, v is 4 and m is 2; and

bridging group (BG) is represented by the formula:

where each G4, the same or different at each occurrence, isindependently carbon, silicon, or germanium, and R¹⁷, the same ordifferent at each occurrence, is each independently a C₁-C₂₀, preferablyC₁-C₈, substituted or unsubstituted linear, branched, or cyclichydrocarbyl group.

Optionally, at least four (alternately all five) of R12, R13, R14, R15,and R16 are each independently a substituted or unsubstituted linear,branched linear, or cyclic C1-C8 hydrocarbyl group, preferably methyl orethyl.

Optionally, R⁴ and R⁵, taken together with the carbon atoms in the firstcyclopentadienyl ring to which they are directly connected, collectivelyform a substituted or unsubstituted ring annelated to the firstcyclopentadienyl ring, such that the metallocene compound is representedby the formula (Z-2):

where, M, X, m, R¹, R², R³, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are as definedfor formula (Z), and

R⁶, R⁷, R¹⁷, and R¹⁸ are each independently hydrogen; a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup; or R⁶ and R⁷, R⁷ and R¹⁷, or R¹⁷ and R¹⁸, taken together with thecarbon atoms in the indenyl ring to which they are directly connected,collectively form one or more substituted or unsubstituted ringsannelated to the indenyl ring.

[1] In formula (Z), (Z-1) or (Z-2):

-   -   i) at least three of R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ if present are        not hydrogen;    -   ii) two or more of R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ if present        together form a fused ring or ring system;    -   iii) at least two of R⁶, R⁷, R¹⁷, and R¹⁸ are hydrogen;    -   iv) each X is independently a halogen or a substituted or        unsubstituted linear, branched linear, or cyclic C₁-C₆        hydrocarbyl group;    -   v) M comprises Zr or Hf;    -   or a combination thereof.        [2] Optionally, one of R¹, R², and R³ is a substituted or        unsubstituted linear, branched (such as branched linear), or        cyclic C₁-C₆ hydrocarbyl group, and two of R¹, R², and R³ are        each a hydrogen. In other particular embodiments, one of R¹ and        R³ is a substituted or unsubstituted linear, branched (such as        branched linear), or cyclic C₁-C₆ hydrocarbyl group, R² is a        hydrogen, and one of R¹ and R³ is a substituted or unsubstituted        linear, branched (such as branched linear), or cyclic C₁-C₆        hydrocarbyl group, or, taken together with R¹⁶, is a bridging        group connecting the first and second cyclopentadienyl rings.        [3] Preferably, R² is hydrogen.        [4] Preferably, each R¹, R², and R³ is, independently, hydrogen        or a substituted or unsubstituted linear, branched (such as        branched linear), or cyclic C₁-C₆ hydrocarbyl group (e.g., a        methyl, an ethyl, a propyl, a butyl, a cyclohexyl, or a phenyl).        When BG (formula Z-1) is present, R² is preferably hydrogen or a        C₂ to C₅ hydrocarbyl group (e.g., an ethyl, a propyl, a butyl, a        pentyl, a hexyl (such as cyclohexyl), a heptyl, an octyl, or a        phenyl).        [5] In some embodiments, one of R¹, R², and R³ is a substituted        or unsubstituted linear, branched (such as branched linear), or        cyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, an ethyl, a        propyl, a butyl, a cyclohexyl, or a phenyl, such as methyl), and        (the other) two of R¹, R², and R³ are each a hydrogen.        [6] In some embodiments, R¹ and R³ are each individually a        substituted or unsubstituted linear, branched (such as branched        linear), or cyclic C₂-C₆ hydrocarbyl group (e.g., an ethyl, a        propyl, a butyl, a cyclohexyl, or a phenyl), and R² is a        hydrogen. In another embodiment, R¹ and R³ are each a methyl        group and R² is a hydrogen.        [7] In some embodiments, R⁴ and R⁵, taken together with the        carbon atoms in the first cyclopentadienyl ring to which they        are directly connected, collectively form a substituted or        unsubstituted phenyl ring annelated to the first        cyclopentadienyl ring. In such embodiments, the four phenyl ring        carbons not connected to the first cyclopentadienyl ring are        each independently bonded to a hydrogen or a substituted or        unsubstituted linear, branched (such as branched linear), or        cyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, an ethyl, a        propyl, a butyl, a cyclohexyl, or a phenyl). In some such        embodiments, at least two (e.g., at least three or all four) of        the four phenyl ring carbons not connected to the first        cyclopentadienyl ring are connected to a hydrogen.        [8] In some embodiments, R⁴ and R⁵, taken together with the        carbon atoms in the first cyclopentadienyl ring to which they        are directly connected, collectively form a substituted or        unsubstituted naphthenyl ring annelated to the first        cyclopentadienyl ring.        [9] In any embodiment of any formula (Z), (Z-1), or (Z-2), BG is        a bridging group represented by the formula: R*₂C, R*₂Si, R*₂Ge,        R*₂CCR*₂, R*₂CCR*₂CR*₂, R*₂CCR*₂CR*₂CR*₂, R*C═CR*, R*C═CR*CR*₂,        R*₂CCR*═CR*CR*₂, R*C═CR*CR*═CR*, R*C═CR*CR*₂CR*₂, R*₂CSiR*₂,        R*₂SiSiR*₂, R*₂SiOSiR*₂, R*₂CSiR*₂CR*₂, R*₂SiCR*₂SiR*₂,        R*C═CR*SiR*₂, R*₂CGeR*₂, R*₂GeGeR*₂, R*₂CGeR*₂CR*₂,        R*₂GeCR*₂GeR*₂, R*₂SiGeR*₂, R*C═CR*GeR*₂, where R* is hydrogen        or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,        halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl        substituent and optionally two or more adjacent R* may join to        form a substituted or unsubstituted, saturated, partially        unsaturated or aromatic, cyclic or polycyclic substituent.        Preferred examples for the bridging group BG include CH₂,        CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(Ph-SiMe₃)₂, and        Si(CH₂)₄. In a preferred embodiment of the invention in any        embodiment of any formula described herein, BG is represented by        the formula ER^(d) ₂ or (ER^(d) ₂)₂, where E is C, Si, or Ge,        and each R^(d) is, independently, hydrogen, halogen, C₁ to C₂₀        hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl,        hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁        to C₂₀ substituted hydrocarbyl, and two R^(d) can form a cyclic        structure including aromatic, partially saturated, or saturated        cyclic or fused ring system. Preferably, BG is a bridging group        comprising carbon or silica, such as dialkylsilyl, preferably BG        is selected from CH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, Me₂Si—SiMe₂,        cyclotrimethylenesilylene (Si(CH₂)₃),        cyclopentamethylenesilylene (Si(CH₂)₅) and        cyclotetramethylenesilylene (Si(CH₂)₄).        [10] Optionally the metallocene compound is not represented by        the formula

where M, X and m are as defined for formula (Z).

The metallocene compound used in processes of the present disclosure formaking PAOs preferably has a structure represented by formula (MC-I)and/or formula (MC-II).

In at least one embodiment, the metallocene compound is preferablyrepresented by formula (MC-III):

wherein: each of R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², M, X,and m can be as described above; R¹⁹ and R²⁰ comprise Group 14 atoms,such as C, Ge, or Si (such as R¹⁹ is C and R²⁰ is C or Si); and R²¹,R²², and R²³ are each independently hydrogen or a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group andat least two of R²¹, R²², and R²³ each independently a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group,wherein at least two of R²¹, R²², and R²³ are a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group,where examples of C₁-C₂₀ substituted or unsubstituted linear, branched,or cyclic hydrocarbyl groups can be as described above.

In some embodiments, the metallocene compound can be represented byformula (MC-1), (MC-2), (MC-3), (MC-4), (MC-5), (MC-6), (MC-7), (MC-8),(MC-9), (MC-10), (MC-11), (MC-12), or (MC-13):

wherein: each of X, M, and m can be as described above.

In some embodiments, the catalyst compound is represented by the formula(MC-IV):

wherein: each of R¹, R², R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹¹, R¹², M, X, and m canbe as described above; and R²⁴, R²⁵, R²⁶, and R²⁷ can be independently ahydrogen or a substituted or unsubstituted linear, branched, or cyclicC₁-C₂₀ hydrocarbyl group.

In at least one embodiment of formula (MC-IV), (i) one of R¹, R², and R³is an alpha Group 14 atom directly attached to the indenyl ring, and abeta Group 14 atom attached to the alpha atom, and two or more, such asthree, substituted or unsubstituted linear, branched, or cyclic C₁-C₈hydrocarbyl groups attached to the beta atom, optionally two of R¹, R²,and R³ are each hydrogen; and/or (ii) each of R⁴, R⁵, R²⁴, R²⁵, R²⁶, andR²⁷ is independently a hydrogen or a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₂₀ hydrocarbyl group; and/or (iii) R⁸,R⁹, R¹⁰, and R¹¹ are each independently a hydrogen, or a substituted orunsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group;and/or (iv) R¹² is a hydrogen, a substituted or unsubstituted linear,branched, or cyclic C₁-C₂₀ hydrocarbyl group or silylcarbyl group;and/or (v) each X is independently a halogen, a hydride, an amide, analkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, anether, or a C₁-C₂₀ substituted or unsubstituted linear, branched, orcyclic hydrocarbyl group, or two or more X moieties together form afused ring or ring system; and/or (vi) M is a transition metal, such asa group 3, 4, or 5 transition metal, such as a group 4 transition metal,such as Hf, Ti, or Zr; and/or (vii) m is an integer equal to 1, 2 or 3,such as 2.

In some embodiments of formula (MC-IV), R⁴, R⁵, R²⁴, R²⁵, R²⁶, and R²⁷are each independently a hydrogen or a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, anethyl, a propyl, a butyl, a cyclohexyl, or a phenyl), optionally R¹ andR²⁷ are not both hydrocarbyl groups.

In some embodiments of formula (MC-IV), at least two (e.g., at leastthree, at least four, at least five, or all six) of R⁴, R⁵, R²⁴, R²⁵,R²⁶, and R²⁷ are a hydrogen. Alternately, in some embodiments of formula(MC-IV), both R¹ and R²⁷ are hydrocarbyl, alternately C₁ to C₁₂hydrocarbyl. Alternately, in some embodiments of formula (MC-IV), bothR¹ and R²⁷ are not hydrocarbyl.

In some embodiments, the catalyst compound is represented by formula(MC-I), (MC-II) (MC-III), or (MC-IV), wherein:

-   -   i) according to formula (MC-I): a first one of R¹ and R³ is a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group; a second one of R¹, R², and R³ is a hydrogen;        the third one of R¹, R², and R³ is a hydrogen; R⁴, R⁵, R⁶, and        R⁷ are each independently hydrogen, a substituted or        unsubstituted linear, branched, or cyclic C₁-C₃₀ hydrocarbyl        group; and R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each independently a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group or R¹² may be a substituted or unsubstituted        linear, branched, or cyclic C₁-C₂₀, such as C₁-C₈, hydrocarbyl        group or silylcarbyl group;    -   ii) according to formula (MC-II): one of R¹ and R³ is a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group; two of R¹, R², and R³ are each hydrogen; R⁴,        R⁷, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each independently        hydrogen, a substituted or unsubstituted linear, branched, or        cyclic C₁-C₃₀ hydrocarbyl group, or two of R⁴, R⁷, R¹³, R¹⁴,        R¹⁵, R¹⁶, R¹⁷, and R¹⁸ taken together with the carbon atoms in        the cyclopentan-indenyl ring to which they are directly        connected, collectively form one or more substituted or        unsubstituted rings fused to the cyclopentan-indenyl ring; and        R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each independently a substituted        or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl        group;    -   iii) according to formula (MC-III): R¹ and R² are hydrogen; R¹⁹        and R²⁰ comprise Group 14 atoms, such as C, Ge, and Si; R²¹,        R²², and R²³ are each independently hydrogen or a substituted or        unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl        group, wherein at least two of R²¹, R²², and R²³ are a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group; R⁴, R⁵, R⁶, and R⁷ are each independently        hydrogen, a substituted or unsubstituted linear, branched, or        cyclic C₁-C₃₀ hydrocarbyl group, or two of R⁴, R⁵, R⁶, and R⁷        taken together with the carbon atoms in the indenyl ring to        which they are directly connected, collectively form one or more        substituted or unsubstituted rings fused to the indenyl ring;        and R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each independently a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group; or    -   iv) according to formula (MC-IV): one of R¹ and R³ is a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group; two of R¹, R², and R³ are each hydrogen; R⁴,        R⁵, R²⁴, R²⁵, R²⁶, and R²⁷ are each independently hydrogen, a        substituted or unsubstituted linear, branched, or cyclic C₁-C₃₀        hydrocarbyl group, or two of R⁴, R⁵, R²⁴, R²⁵, R²⁶, and R²⁷        taken together with the carbon atoms in the benzindenyl ring to        which they are directly connected, collectively form one or more        substituted or unsubstituted rings fused to the benz-indenyl        ring; and R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each independently a        substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀        hydrocarbyl group;

wherein in the formulae (MC-I), (MC-II), (MC-III), (MC-IV): each X isindependently a halogen, a hydride, an amide, an alkoxide, a sulfide, aphosphide, a diene, an amine, a phosphine, an ether, a C₁-C₂₀substituted or unsubstituted linear, branched, or cyclic hydrocarbylgroup, or two or more X moieties together form a fused ring or ringsystem; M is a transition metal, such as a group 3, 4, or 5 transitionmetal, such as a group 4 transition metal, such as Hf, Ti, or Zr; and mis an integer equal to 1, 2 or 3, such as 2.

In some embodiments, the catalyst compound is represented by formula(MC-2), (MC-3), (MC-4), (MC-5), (MC-6), (MC-7), (MC-8), (MC-9), (MC-10),(MC-11) (MC-12) or (MC-13), wherein: each X is independently a halogen,a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, anamine, a phosphine, an ether, or a C₁-C₂₀ substituted or unsubstitutedlinear, branched, or cyclic hydrocarbyl group, or two or more X moietiesmay together form a fused ring or ring system; M is a transition metal,such as a group 3, 4, or 5 transition metal, such as a group 4transition metal, such as Hf, Ti, or Zr; and m is an integer equal to 1,2 or 3, such as 2.

The metallocene compound used in the process of the present disclosurefor making PAOs generally can have a structure represented by formula(MC-V):

wherein:

each of R¹, R², and R³, R⁸, R⁹, R¹⁰, R¹¹, and R¹², M, X, and m can be asdescribed above; and

R²⁸ and R²⁹ are each independently a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₃₀ hydrocarbyl group, or R²⁸ and R²⁹,taken together with the carbon atoms in the first cyclopentadienyl ringto which they are directly connected, can collectively form one or moresubstituted or unsubstituted rings fused to the first cyclopentadienylring.

In at least one embodiment of formula (MC-V), R²⁸ and R²⁹, takentogether with the carbon atoms in the first cyclopentadienyl ring towhich they are directly connected, can collectively form a substitutedor unsubstituted phenyl ring fused to the first cyclopentadienyl ring.In such embodiments, the four phenyl ring carbons not connected to thefirst cyclopentadienyl ring can each be independently bonded to ahydrogen or a substituted or unsubstituted linear, branched, or cyclicC₁-C₆ hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl). In some such embodiments, at least two (e.g.,at least three or all four) of the four phenyl ring carbons notconnected to the first cyclopentadienyl ring can be connected to ahydrogen.

In at least one embodiment of formula (MC-V), R²⁸ and R²⁹, takentogether with the carbon atoms in the first cyclopentadienyl ring towhich they are directly connected, can collectively form a substitutedor unsubstituted naphthenyl ring fused to the first cyclopentadienylring. In some embodiments, the fused ring or rings may comprisesaturated ring carbons, unsaturated ring compounds, or a combination ofsaturated and unsaturated carbon atoms, for example, a non-aromatic ringor a combination of aromatic and non-aromatic rings.

In at least one metallocene compound formula herein, both the first andsecond Cp rings in the metallocene compound of the present disclosurecan be substituted. In some embodiments, one, and not both, of the firstand second Cp rings can be fused to one or more rings.

In at least one metallocene compound formula herein, one of R¹ and R³ isa beta branched ligand in which a Group 14 atom, e.g., carbon, silicon,germanium, is attached directly to the cyclopentadienyl ring, this sameatom further includes at least two non-hydrogen substituents accordingto the above listing. In other words, the Group 14 atom is tertiary orquaternarily substituted, which includes the bond between thecyclopentadienyl ring and the group 14 atom. Examples include isobutyl,neopentyl, trialkylsilyl, and trialkylgermanyl moieties according toformula (MC-III), wherein R¹⁹ and R²⁰ comprise Group 14 atoms, such ascarbon, silicon and/or germanium (such as R¹⁹ is C and R²⁰ is C or Si),and at least two of R²¹, R²², and R²³ are each independently asubstituted or unsubstituted linear, branched, or cyclic C₁-C₂₀, such asC₁-C₈, hydrocarbyl group.

In at least one metallocene compound formula herein, R⁴, R⁵, R⁶, and R⁷are each independently hydrogen, a substituted or unsubstituted linear,branched, or cyclic C₁-C₃₀ hydrocarbyl group. In at least onemetallocene compound formula herein, R⁴, R⁵, R⁶, and R⁷ are eachindependently hydrogen, a substituted or unsubstituted linear, branched,or cyclic C₁-C₃₀ hydrocarbyl group in which two of R⁴, R⁵, R⁶, and R⁷taken together with the carbon atoms in the indenyl ring to which theyare directly connected, collectively form one or more substituted orunsubstituted rings fused to the indenyl ring. The rings are indicatedby the dotted lines between the respective R group substitutions with aring between R⁴ and R⁵ indicated as Ring 4-5, a ring between R⁵ and R⁶indicated as Ring 5-6 and a ring between R⁶ and R⁷ indicated as Ring 6-7as shown in the general formula (MC-III-A) below:

In some embodiments, R⁵ and R⁶ taken together with the carbon atoms inthe indenyl ring to which they are directly connected, collectively formRing 4-5 comprising a C₃-C₆ ring, such as an alicyclic ring, such as a 5membered ring including two the carbons of the indenyl ring. In suchembodiments, the 3 alicyclic ring carbons not directly part of theindenyl ring are each independently bonded to a hydrogen or asubstituted or unsubstituted linear, branched, or cyclic C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, acyclohexyl, or a phenyl). In some embodiments, at least two or all threeof the alicyclic ring carbons are connected to a hydrogen, one of R′ isa substituted or unsubstituted linear, branched, or cyclic C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, apentyl, an isoamyl, a neopentyl, a cyclohexyl, or a phenyl), and R² ishydrogen.

In some embodiments, at least one of R²¹, R²², or R²³ is C₁-C₆hydrocarbyl group (e.g., a methyl, an ethyl, a propyl, a butyl, apentyl, an isoamyl, a neopentyl, a cyclohexyl, or a phenyl), such thatR³ is a beta-branched moiety. In some embodiments, R¹⁹ and R¹⁹ arecarbon, silicon or germanium, and R²¹, R²², and R²³ are each a C₁-C₆hydrocarbyl group; such as R¹⁹ is a methylene group (—CH₂—) and R²⁰,R²¹, R²² and R²³ form a trimethylsilyl, triethylsilyl, or terphenylsilylmoiety. As an example, and in any of the above embodiments, R⁸, R⁹, R¹⁰,R¹¹, R¹², R⁶, and R⁷ are each independently a hydrogen, or a substitutedor unsubstituted linear, or branched C₁-C₆, hydrocarbyl group. In someembodiments, R⁵ and R⁶ taken together with the carbon atoms in theindenyl ring to which they are directly connected, collectively formRing 5-6 comprising three additional carbons to form a 5 memberedalicyclic ring; R¹, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are methyl radicals, R²,R³, R⁴, and R⁷, are hydrogen. In such embodiments, the metallocenecompound can have a structure represented by formula (MC-3) below:

In some embodiments R⁶ and R⁷ taken together with the carbon atoms inthe indenyl ring to which they are directly connected, collectively formone or more substituted or unsubstituted C₃-C₆ rings fused to theindenyl ring; and R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are eachindependently a hydrogen, or a substituted or unsubstituted linear, orbranched C₁-C₆, hydrocarbyl group. In some embodiments, R⁶ and R⁷ takentogether with the carbon atoms in the indenyl ring to which they aredirectly connected, collectively form a six membered phenyl ring, Ring6-7 comprising four additional carbons. In such embodiments, the fourphenyl ring carbons not directly part of the indenyl ring (the carbonsattached to R²⁴, R²⁵, R²⁶, and R²⁷ in formula (MC-VI) below) are eachindependently bonded to a hydrogen or a substituted or unsubstitutedlinear, branched, or cyclic C₁-C₆ hydrocarbyl group (e.g., a methyl, anethyl, a propyl, a butyl, a cyclohexyl, or a phenyl). In suchembodiments, at least two of, or at least three of, or all four of R²⁴,R²⁵, R²⁶, and R²⁷ are hydrogen. Stated another way, R⁶ and R⁷ takentogether with the carbon atoms in the first cyclopentadienyl ring towhich they are directly connected, collectively form a substituted orunsubstituted naphthenyl ring fused to the first cyclopentadienyl ring.In such embodiments, the metallocene compound can have a structurerepresented by formula (MC-VI) below:

In at least one embodiment, one of R¹ and R¹⁹ are a substituted orunsubstituted linear, branched, or cyclic C₁-C₆ hydrocarbyl group (e.g.,a methyl, an ethyl, a propyl, a butyl, a pentyl, an isoamyl, aneopentyl, a cyclohexyl, or a phenyl), R² and R¹ are hydrogen. In suchan embodiment, R¹⁹ and R²⁰-R²³ form a neopentyl (i.e.,2,2-dimethylpropyl), R¹, R², R⁴, R⁵, R²⁴, R²⁵, R²⁶, and R²⁷ are eachhydrogen, and R⁸, R⁹, R¹⁰, R¹¹, R¹² are methyl; the metallocene compoundcan have a structure represented by formula (III-B) below:

where M is Hf or Zr and M is 2.

In some embodiments, R¹⁹ and R²⁰-R²³ form a methyl-trimethylsilyl,methyl-triethylsilyl, or methyl-triphenylsilyl moiety, R⁴, R⁵, R⁶, andR⁷, are each hydrogen, and or a substituted or unsubstituted linear, orbranched C₁-C₆, hydrocarbyl group. In some embodiments, R⁴, R⁵, R⁶, andR′ are hydrogen, and R⁸, R⁹, R¹⁰, R¹¹, R¹² are methyl; having astructure represented by formula (MC-VI-SI) below.

wherein R¹⁹, R²¹, R²², and R²³ are substituted or unsubstituted linear,branched, or cyclic C₁-C₆ hydrocarbyl group, such as methyl, ethyl, orphenyl, such as each of R¹⁹, R²¹, R²², and R²³ are methyl.

It is noted, in the embodiments listed above, R¹ and R³ may beinterchangeable. Reference to either of R¹ and R³ are maintained forconsistency and clarity herein. In any of the above embodiments, Mcomprises, consists essentially of, or is Zr and/or Hf; m is 2; and eachX is independently a methyl, an ethyl, a propyl, a butyl, a hexyl, anoctyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide.

Example metallocene compounds useful for the process of the presentdisclosure include the following compounds and their optical isomers, ifapplicable (not shown):

Metallocene compounds generally can be synthesized by using typicalchemical reagents (e.g., halides of hafnium, zirconium, titanium) andintermediates (such as ligands containing one or two substituted orunsubstituted Cp rings, substituted or unsubstituted fused Cp ring suchas indenyl rings or benzindenyl rings, and the like) that arecommercially available, and following typical reaction schemesexemplified in various synthesis descriptions, e.g., as described in theexample sections of U.S. Provisional Application Nos. 62/477,683 and62/477,706, both filed Mar. 28, 2017, the contents of each of which arehereby incorporated by reference.

IV. B.2 Activators and Activation of the Metallocene Compound

The catalyst may be activated by any suitable activator such as anon-coordinating anion (NCA) activator. An NCA is an anion which eitherdoes not coordinate to the catalyst metal cation or that coordinatesonly weakly to the metal cation. An NCA coordinates weakly enough that aneutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer, can displace it from the catalyst center. Any metalor metalloid that can form a compatible, weakly coordinating complexwith the catalyst metal cation may be used or contained in the NCA.Suitable metals include aluminum, gold, and platinum. Suitablemetalloids include boron, aluminum, phosphorus, and silicon.

Lewis acid and ionic activators may also be used. Useful butnon-limiting examples of Lewis acid activators include triphenylboron,tris-perfluorophenylboron, and tris-perfluorophenylaluminum. Useful butnon-limiting examples of ionic activators include dimethylaniliniumtetrakisperfluorophenylborate, triphenylcarbeniumtetrakisperfluorophenylborate, and dimethylaniliniumtetrakisperfluorophenylaluminate.

An additional subclass of useful NCAs comprises stoichiometricactivators, which can be either neutral or ionic. Examples of neutralstoichiometric activators include trisubstituted boron, tellurium,aluminum, gallium and indium or mixtures thereof. The three substituentgroups are each independently selected from alkyls, alkenyls, halogen,substituted alkyls, aryls, arylhalides, alkoxy, and halides. Forexample, the three groups can be independently selected from halogen,mono or multicyclic (including halosubstituted) aryls, alkyls, andalkenyl compounds and mixtures thereof, for example alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to20 carbon atoms (including substituted aryls). For example, the threegroups can be alkyls having 1 to 4 carbon groups, phenyl, naphthyl, ormixtures thereof. For example, the three groups are halogenated, such asfluorinated, aryl groups. Ionic stoichiometric activator compounds maycontain an active proton, or some other cation associated with, but notcoordinated to, or only loosely coordinated to, the remaining ion of theionizing compound.

Ionic catalysts can be prepared by reacting a transition metal compoundwith an activator, such as B(C₆F6)₃, which upon reaction with thehydrolyzable ligand (X′) of the transition metal compound forms ananion, such as ([B(C₆F₅)₃(X′)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts can beprepared with activator components which are ionic compounds orcompositions. Additionally or alternatively, activators can be preparedutilizing neutral compounds.

Compounds used as an activator component in the preparation of the ioniccatalyst systems used in a process of the present disclosure can includea cation, which can be a Brønsted acid capable of donating a proton, anda compatible NCA which anion is relatively large (bulky), capable ofstabilizing the active catalyst species which is formed when the twocompounds are combined and said anion will be sufficiently labile to bedisplaced by olefinic, diolefinic, and acetylenically unsaturatedsubstrates or other neutral Lewis bases such as ethers or nitriles.

In at least one embodiment, the ionic stoichiometric activators includea cation and an anion component, and may be represented by the followingformula:(L**-H)_(d) ⁺(A_(d) ⁻)wherein:

L** is an neutral Lewis base;

H is hydrogen;

(L**-H)⁺ is a Brønsted acid or a reducible Lewis acid; and

A^(d−) is an NCA having the charge d−, and d is an integer from 1 to 3.

The cation component, (L**-H)_(d) ⁺ may include Brønsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thecatalyst after alkylation.

The activating cation (L**-H)_(d) ⁺ may be a Brønsted acid, capable ofdonating a proton to the alkylated transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, such as ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N.N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers such asdimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L**-H)_(d) ⁺ may also be amoiety such as silver, tropylium, carbeniums, ferroceniums and mixtures,such as carbeniums and ferroceniums; such as triphenyl carbenium. Theanion component A_(d) ⁻ includes those having the formula [Mk+Qn]_(d) ⁻wherein k is an integer from 1 to 3; n is an integer from 2-6; n−k=d; Mis an element selected from Group 13 of the Periodic Table of theElements, such as boron or aluminum, and Q is independently a hydride,bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having upto 20 carbon atoms with the proviso that in not more than one occurrenceis Q a halide. For example, each Q is a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group,such as each Q is a pentafluoryl aryl group. Examples of suitable A_(d)⁻ also include diboron compounds as disclosed in U.S. Pat. No.5,447,895, which is incorporated herein by reference.

Boron compounds which may be used as an NCA activator in combinationwith a co-activator are trisubstituted ammonium salts such as:trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(tert-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,dimethyl(tert-butyl) ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,and dialkyl ammonium salts such as: di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and other salts such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, andbenzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

In at least one embodiment, the NCA activator, (L**-H)_(d) ⁺(A_(d) ⁻),is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N.N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

In at least one embodiment, the activator is selected from Lewis acidactivators such as triphenylboron, tris-perfluorophenylboron,tris-perfluorophenylaluminum and the like and or ionic activators suchas N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,triphenylcarbonium tetrakis(perfluorophenyl)borate, triphenylcarboniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)aluminate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)aluminate, and the like.

Pehlert et al., U.S. Pat. No. 7,511,104 provides additional details onNCA activators that may be useful, and these details are herebyincorporated by reference.

Additional activators that may be used include alumoxanes or alumoxanesin combination with an NCA. In one embodiment, alumoxane activators areutilized as an activator. Alumoxanes are generally oligomeric compoundscontaining —Al(R′)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators, such aswhen the abstractable ligand is an alkyl, halide, alkoxide or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused.

A catalyst co-activator is a compound capable of alkylating thecatalyst, such that when used in combination with an activator, anactive catalyst is formed. Co-activators may include alumoxanes such asmethylalumoxane, modified alumoxanes such as modified methylalumoxane,and aluminum alkyls such trimethylaluminum, tri-isobutylaluminum,triethylaluminum, tri-isopropylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tri-n-decylaluminum, and tri-n-dodecylaluminum.Co-activators are typically used in combination with Lewis acidactivators and ionic activators when the catalyst is not a dihydrocarbylor dihydride complex.

The co-activator may also be used as a scavenger to deactivateimpurities in feed or reactors. A scavenger is a compound that issufficiently Lewis acidic to coordinate with polar contaminates andimpurities adventitiously occurring in the polymerization feedstocks orreaction medium. Such impurities can be inadvertently introduced withany of the reaction components, and adversely affect catalyst activityand stability. Scavenging compounds may be organometallic compounds suchas triethyl aluminum, triethyl borane, tri-isobutyl aluminum,methylalumoxane, isobutyl aluminumoxane, tri-n-hexyl aluminum,tri-n-octyl aluminum, and those having bulky substituents covalentlybound to the metal or metalloid center being exemplary to minimizeadverse interaction with the active catalyst. Other useful scavengercompounds may include those mentioned in U.S. Pat. No. 5,241,025; EP-A0426638; and WO 1997/022635, which are hereby incorporated by referencefor such details.

U.S. Pat. No. 9,409,834 (e.g., at line 39, column 21 to line 44, column26) provides a detailed description of the activators and coactivatorsthat may be used with the metallocene compound in the catalyst system ofthe present disclosure. The relevant portions of this patent areincorporated herein by reference in their entirety. Additionalinformation of activators and co-activators that may be used with themetallocene compounds in the catalyst system of the present disclosurecan be found in US Patent Application Publication No. 2013/0023633(e.g., at paragraph [0178] page 16 to paragraph [0214], page 22). Therelevant portions of this reference are incorporated herein by referencein their entirety.

The reaction time or reactor residence time can be dependent on the typeof catalyst used, the amount of catalyst used, and the desiredconversion level. Different transition metal compounds (also referred toas metallocene) have different activities. A high amount of catalystloading tends to give high conversion at short reaction time. However, ahigh amount of catalyst usage can make the production processuneconomical and difficult to manage the reaction heat or to control thereaction temperature. Therefore, it is useful to choose a catalyst withmaximum catalyst productivity to minimize the amount of metallocene andthe amount of activators needed. For a catalyst system of metalloceneplus a Lewis Acid or an ionic promoter with NCA component, thetransition metal compound used may be from about 0.01 microgram to about500 micrograms of metallocene component/gram of alpha-olefin feed, suchas from about 0.1 microgram to about 100 microgram of metallocenecomponent per gram of alpha-olefin feed. Furthermore, the molar ratio ofthe NCA activator to metallocene can be from about 0.1 to about 10, suchas about 0.5 to about 5, such as about 0.5 to about 3. For theco-activators of alkylaluminums, the molar ratio of the co-activator tometallocene can be from about 1 to about 1,000, such as about 2 to about500, such as about 4 to about 400.

In selecting oligomerization conditions, to obtain the desired firstreactor effluent, the system uses the transition metal compound (alsoreferred to as the catalyst), activator, and co-activator. US2007/0043248 and US 2010/029242 provide additional details ofmetallocene catalysts, activators, co-activators, and appropriate ratiosof such compounds in the feedstock that may be useful, and theseadditional details are hereby incorporated by reference.

IV. B.3 Scavengers for the First Oligomerization

A scavenger can be an additional component of a catalyst systemdescribed herein. A scavenger is a compound typically added tofacilitate oligomerization or polymerization by scavenging impurities.Some scavengers may also act as activators and may be referred to asco-activators. A co-activator which is not a scavenger may also be usedin conjunction with an activator in order to form an active catalystwith a transition metal compound. In some embodiments, a co-activatorcan be pre-mixed with the transition metal compound to form an alkylatedtransition metal compound, also referred to as an alkylated catalystcompound or alkylated metallocene. To the extent scavengers facilitatethe metallocene compound in performing the intended catalytic function,scavengers, if used, are sometimes considered as a part of the catalystsystem.

U.S. Pat. No. 9,409,834 (e.g., at line 37, column 33 to line 61, column34) provides detailed description of scavengers useful in the process ofthe present disclosure for making PAO. The relevant portions in thispatent on scavengers, their identities, quantity, and manner of use areincorporated herein in their entirety.

IV. C Process for Making PAO

IV. C.1 Monomer(s)

The alpha-olefin feed for making the PAO materials of the presentdisclosure may comprise one or more of C₆-C₃₂ alpha-olefins (such asC₆-C₂₄, such as C₆-C₁₈, C₈-C₁₈, or C₆-C₁₂). The alpha-olefin feed maycomprise ethylene, propylene, C₄ alpha-olefins, and C₅ alpha-olefins. Incertain embodiments, each of ethylene, propylene, C₄ alpha-olefins(1-butene and 2-methyl-1-propene), and C₅ alpha-olefins (1-pentene andvarious isomers of methyl-1-butene) is supplied to the polymerizationreactor, each independently at no higher than c1 mol %, based on thetotal moles of the alpha-olefins supplied to the polymerization reactor,where c1 can be 25, 20, 10, 5, 4, 3, 2, 1, 0.5, 0.1, or 0.01, for eachmonomer; additionally or alternatively, any combination of C₂-C₅alpha-olefins (including two or more, three or more, or all four ofethylene, propylene, C₄ alpha-olefins, and C₅ alpha-olefins) aresupplied to the polymerization reactor collectively at no higher than c1mol %, based on the total moles of the alpha-olefins supplied to thepolymerization reactor. In some embodiments, the alpha-olefin feed issubstantially free of ethylene, propylene, C₄ alpha-olefins, and C₅alpha-olefins (or completely free of intentionally added C₂-C₅alpha-olefins, allowing for impurities present in other feedcomponents). In some embodiments, substantially all alpha-olefins in thefeed are C₆-C₃₀ (e.g., C₆-C₂₄, such as C₆-C₁₁, C₈-C₁₈, or C₆-C₁₂)alpha-olefins. “Substantially all” means at least 90 mol % (e.g., atleast about 92 mol %, at least about 94 mol %, at least about 95 mol %,at least about 96 mol %, at least about 98 mol %, at least about 99%, atleast about 99.5 mol %, or completely all, allowing for some impuritiespresent in feed components), based on the total moles of thealpha-olefins present in the feed. In some embodiments, any combinationof C₂-C₅ alpha-olefins are collectively present in the alpha-olefin feedat no higher than c1 mol %, (where c1 can be about 25, about 20, about10, about 5, about 4, about 3, about 2, about 1, about 0.5, about 0.1,or about 0.01), based on the total moles of the alpha-olefins suppliedto the polymerization reactor.

In some embodiments, at least a portion (e.g., at least about 80 mol %,at least about 85 mol %, at least about 90 mol %, at least about 95 mol%, at least about 96 mol %, at least about 98 mol %, at least about 99mol %, at least about 99.5 mol %, or completely all, allowing for someimpurities present in feed components) of the alpha-olefins present inthe feed are linear alpha-olefins (LAOs), i.e., those without a branchattached to the carbon backbone thereof. Non-limiting examples of LAOsare 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-octadecene, 1-icocene, C₂₂, C₂₄, C₂₆,C₂₈, C₃₀ and C₃₂ LAOs, and a combination thereof. Without being bound bytheory, PAO products made from such LAOs by using the process of thepresent disclosure can tend to have fewer branches and pendant groups,leading to generally more uniform PAO molecular structures.

Where a single alpha-olefin is fed to the polymerization reactor, thethus obtained PAO is a homopolymer. Homopolymers can have substantiallyuniform molecular structure, and accordingly desirable physical andrheological properties such as viscosity index. A homopolymer can tendto have pendant groups attached to the carbon backbone with highlyuniform length.

In certain situations, a mixture of two, three, or even morealpha-olefins in the feed may be desired to produce a copolymer PAOproduct. To that end, alpha-olefins with the following combinations canbe advantageous: C₆/C₈, C₆/C₁₀, C₆/C₁₂, C₆/C₁₄, C₆/C₁₆, C₈/C₁₀, C₈/C₁₂,C₈/C₁₄, C₈/C₁₆, C₁₀/C₁₂, C₁₀/C₁₄, C₁₀/C₁₆, C₁₀/C₁₈, C₁₂/C₁₄, C₁₂/C₁₆,C₁₂/C₁₈, C₁₂/C₂₀, C₆/C₈/C₁₀, C₆/C₈/C₁₂, C₆/C₈/C₁₄, C₆/C₁₀/C₁₂,C₆/C₁₀/C₁₄, C₈/C₁₀/C₁₂, C₈/C₁₀/C₁₄, C₈/C₁₂/C₁₄, C₁₀/C₁₂/C₁₆,C₁₀/C₁₂/C₁₈, C₁₀/C₁₄/C₁₆, C₁₀/C₁₄/C₁₈, and the like. In someembodiments, at least one of the alpha-olefins in the mixture feed canbe an LAO. In some embodiments, substantially all of the alpha-olefinsin the mixture feed can be LAOs.

In some embodiments, alpha-olefin monomers are mono-olefins containingone C═C bond per monomer molecule, though those olefins containing twoor more C═C bonds per monomer molecule can be used as well.

In some embodiments, monomers useful herein include substituted orunsubstituted C₆ to C₃₂ alpha-olefins, or C₆ to C₂₀ alpha-olefins, or C₆to C₁₄ alpha-olefins, or hexene, heptene, octene, nonene, decene,undecene, dodecene, tetradecene and isomers thereof. In someembodiments, the poly alpha-olefin prepared herein comprises about 50mol % or more (such as about 60 mol % or more, such as about 70 mol % ormore, such as about 80 mol % or more, such as about 90 mol % or more,such as about 99 mol % or more) of one or more C₆ to C₃₂ (such as C₆ toC₂₀, such as C₈ to C₁₈) alpha-olefin monomers.

Useful C₆ to C₃₂ alpha-olefin monomers include hexene, heptane, octene,nonene, decene, undecene, dodecene, tetradecene, substituted derivativesthereof, and isomers thereof.

In some embodiments, the monomers comprise C₆ to C₂₀ alpha-olefins, orC₆ to C₁₄ alpha-olefins, and/or C₅ to C₁₂ alpha-olefins.

In some embodiments, olefin monomers include one (alternately two,alternately three) or more of hexene, heptene, octene, nonene, decene,dodecene, and tetradecene.

In an embodiment the PAO is a homopolymer of any C₈ to C₁₂ alpha-olefin,i.e., the PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene or 1-tetradecene. In someembodiments, the PAO is a homopolymer of decene. In at least oneembodiment the PAO is a copolymer comprising decene and one or more ofany of the monomers listed above.

In an embodiment, the PAO comprises two or more monomers, or three ormore monomers, or four or more monomers, or five or more monomers. Forexample, a C₈, C₁₀, C₁₂-linear alpha-olefin mixture, or a C₆, C₇, C₈,C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄-linear alpha-olefin mixture, or a C₆, C₈,C₁₀, C₁₂, C₁₄, C₁₆, C₁₈-linear alpha-olefin mixture can be used as afeed.

In at least one embodiment, the PAO comprises less than about 50 mol %of C₂, C₃, and C₄ monomers, or less than about 40 mol %, or less thanabout 30 mol %, or less than about 20 mol %, or less than about 10 mol%, or less than about 5 mol %, or less than about 3 mol %, or about 0mol %. Specifically, in at least one embodiment, the PAO comprises lessthan about 50 mol % of ethylene, propylene and butene, or less thanabout 40 mol %, or less than about 30 mol %, or less than about 20 mol%, or less than about 10 mol %, or less than about 5 mol %, or less thanabout 3 mol %, or about 0 mol %. In at least one embodiment, the PAOcomprises less than about 40 mol %, or less than about 20 mol %, or lessthan about 10 mol %, or less than about 5 mol %, or less than about 3mol %, or about 0 mol % of ethylene.

In at least one embodiment, the PAO comprises less than 25 mol % of C₂,C₃, and C₄ monomers, or less than about 20 mol %, or less than about 15mol %, or less than about 10 mol %, or less than about 5 mol %, or lessthan about 1 mol %, or about 0 mol %. Specifically, in at least oneembodiment, the PAO comprises less than about 25 mol % of ethylene,propylene and butene, or less than about 20 mol %, or less than about 15mol %, or less than about 10 mol %, or less than about 5 mol %, or lessthan about 1 mol %, or about 0 mol %. In at least one embodiment, thePAO comprises less than about 25 mol %, or less than about 20 mol %, orless than about 10 mol %, or less than about 5 mol %, or less than about1 mol %, or about 0 mol % of ethylene.

In at least one embodiment, the PAO comprises less than about 40 mol %of propylene. In at least one embodiment, the PAO comprises less thanabout 40 mol % of butene. In at least one embodiment, the PAO comprisesless than about 10 mol % of ethylene. In at least one embodiment, thePAO comprises less than about 10 mol % of propylene. In at least oneembodiment, the PAO comprises less than about 10 mol % of butene.

In at least one embodiment, the PAO comprises less than about 25 mol %of propylene. In at least one embodiment, the PAO comprises less thanabout 25 mol % of butene. In at least one embodiment, the PAO comprisesless than about 5 mol % of ethylene. In at least one embodiment, the PAOcomprises less than about 5 mol % of propylene. In at least oneembodiment, the PAO comprises less than about 5 mol % of butene. In atleast one embodiment, the PAO comprises less than about 1 mol % ofethylene. In at least one embodiment, the PAO comprises less than about1 mol % of propylene. In at least one embodiment, the PAO comprises lessthan about 1 mol % of butene.

The alpha-olefins used herein can be produced directly from ethylenegrowth process as practiced by several commercial production processes,or they can be produced from Fischer-Tropsch hydrocarbon synthesis fromCO/H₂ syngas, or from metathesis of internal olefins with ethylene, orfrom cracking of petroleum or Fischer-Tropsch synthetic wax at hightemperature, or any other alpha-olefin synthesis routes. An exemplaryfeed for this disclosure can be at least 80 wt % alpha-olefin (such aslinear alpha-olefin), such as at least 90 wt % alpha-olefin (such aslinear alpha-olefin), or approximately 100% alpha-olefin (such as linearalpha-olefin). However, alpha-olefin mixtures can also be used as feedsin this disclosure, especially if the other components areinternal-olefins, branched olefins, paraffins, cyclic paraffins,aromatics (such as toluene and or xylenes). These components may havediluent effects and are believed to not have a substantial detrimentaleffect on the polymerization of alpha-olefins. In other words, theprocess described herein can selectively convert alpha-olefins in amixture and leave the other components largely, if not completely,unreacted. This can be useful when ethylene is not present in themixture. This technology can be used to separate out alpha-olefins froma mixture by selectively reacting them with polymerization oroligomerization catalyst systems, effectively if not completelyeliminating the need to separate alpha-olefins from the remainder of thecomponents in a mixed feed stream. This can be economicallyadvantageous, for example, in a process utilizing Fisher-Tropschsynthesis olefin product streams containing alpha-olefins,internal-olefins and branched olefins. Such a mixture can be fed tooligomerization technology as described herein and to selectively reactaway the alpha-olefin. No separate step to isolate the alpha-olefin maybe needed. Another example of the utility of this process involvesalpha-olefins produced by the metathesis of internal olefins withethylene, which may contain some internal olefins. This mixed olefinbase stock feed can be reacted as-is in thepolymerization/oligomerization process of the present disclosure, whichselectively converts the alpha-olefins into lube products. Thus, one canuse the alpha-olefin for the base stock synthesis without having toseparate the alpha-olefin from internal olefin. This can bring asignificant improvement in process economics. The feed olefins can bethe mixture of olefins produced from other linear alpha-olefin processcontaining C₄ to C₂₀ alpha-olefins as described in Chapter 3 “Routes toAlpha-Olefins” of the book Alpha Olefins Applications Handbook, Editedby G. R. Lappin and J. D. Sauer, published by Marcel Dekker, Inc. N.Y.1989.

IV. C.2 Feed Purification

Olefin feed and or solvents may be treated to remove catalyst poisons,such as peroxides, oxygen, or nitrogen-containing organic compounds oracetylenic compounds before being supplied to the polymerizationreactor. For example, the treatment of the linear alpha-olefin with anactivated 13 Å molecular sieve and a de-oxygenate catalyst (i.e., areduced copper catalyst) can increase catalyst productivity (expressedin terms of quantity of PAO produced per micromole of the metallocenecompound used) more than 10-fold. Alternatively, the feed olefins and orsolvents may be treated with an activated molecular sieve, such as 3 Å,4 Å, 8 Å, or 13 Å molecular sieve, and/or in combination with anactivated alumina or an activated de-oxygenate catalyst. Such treatmentcan increase catalyst productivity 2- to 10-fold or more.

IV. C.3 Polymerization Reaction

Many polymerization/oligomerization processes and reactor types used formetallocene-catalyzed polymerization or oligomerization such assolution, slurry, and bulk polymerization or oligomerization processedcan be used in this present disclosure. If a solid or supported catalystis used, a slurry or continuous fixed bed or plug flow process may besuitable. In some embodiments, the monomers are contacted with themetallocene compound and the activator in the solution phase, bulkphase, or slurry phase, for example in a continuous stirred tank reactoror a continuous tubular reactor. In some embodiments, the temperature inany reactor used herein can be from about −10° C. to about 250° C.,e.g., from about 30° C. to about 220° C., such as from about 50° C. toabout 180° C., from about 60° C. to about 170° C., or from about 70° C.to about 150° C. In some embodiments, the pressure in any reactor usedherein can be from about 0.1 to about 100 atmospheres, e.g., from about0.5 to about 75 atmospheres or from about 1 to about 50 atmospheres.Alternatively, the pressure in any reactor used herein can be from about1 to about 50,000 atmospheres, e.g., from about 1 to about 25,000atmospheres. Additionally or alternatively, the monomer(s), metalloceneand activator can be contacted for a residence time of about 1 second toabout 100 hours, e.g., about 30 seconds to about 50 hours, about 2minutes to about 6 hours, or about 1 minute to about 4 hours.Additionally or alternatively, solvent or diluent may be present in thereactor and may include butanes, pentanes, hexanes, heptanes, octanes,nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes,pentadecanes, hexadecanes, toluene, o-xylene, m-xylene, p-xylene, mixedxylenes, ethylbenzene, propylbenzenes such as isopropylbenzene,butylbenzenes such as n-butylbenzene or t-butylbenzene, cumene, or acombination thereof; solvents can include toluene, xylenes,ethylbenzene, normal paraffins (such as NORPAR® solvents available fromExxonMobil Chemical Company in Houston, Tex.), isoparaffin solvents(such as ISOPAR® solvents available from ExxonMobil Chemical Company inHouston, Tex.), or a combination thereof. These solvents or diluents maytypically be pre-treated in same manners as the feed olefins.

Regardless of the type of reactor or process, it can be desired that theaverage activity level of the catalyst system be maintained at or abovea sufficiently high level, so as to attain a minimum reasonable yield ofoligomeric product, relative to monomeric reactant(s). For example, insome embodiments, the catalytic reaction can have an average activitylevel of at least about 800 g/s·mol, e.g., at least about 900 g/s·mol,at least about 1000 g/s·mol, at least about 1100 g/s·mol, at least about1200 g/s·mol, at least about 1300 g/s·mol, at least about 1400 g/s·mol,at least about 1500 g/s·mol, at least about 1700 g/s·mol, at least about1900 g/s·mol, at least about 2100 g/s·mol, at least about 2500 g/s·mol,or at least about 2800 g/s·mol; although average activity levels are notoften characterized as being “too high,” it is theoretically possiblefor the average activity level to be so high that control of thereaction product may be difficult to achieve in practice, such that theaverage catalytic reaction activity level can optionally be less thanabout 1000 kg/s·mol, e.g., less than about 500 kg/s·mol, in someembodiments. Additionally or alternatively, in some embodiments, thecatalytic reaction can provide a minimum reasonable yield (grams ofoligomer per grams of monomer feed) of at least about 18%, e.g., atleast about 19%, at least about 20%, at least about 22%, at least about24%, at least about 27%, at least about 30%, at least about 33%, atleast about 36%, at least about 38%, or at least 40%, based on areaction time of about 1 h (about 3600 s); although reasonable catalyticyield is not often characterized as being “too high,” with a maximum ofapproximately 100% in a 1-h reaction time, it is theoretically possiblefor relatively high yields, such as high yields in relatively shortreaction times, to detrimentally affect the ability to control thereaction product, e.g., such that a maximum reasonable yield mayoptionally be approximately 100% in a reaction time of about 1 minute orless, e.g., approximately about 100% in a reaction time of about 10minutes or less, approximately 100% in a reaction time of about 30minutes or less, approximately 100% in a reaction time of about 1 h orless, approximately about 95% in a reaction time of about 1 hour orless, or approximately 90% in a reaction time of about 1 hour or less.

In some embodiments, it can be desirable to attain both relatively lowproduct molecular weight and relatively high product vinylidene content.However, in many metallocene reactions where a vinylidene bond is asignificant unsaturation product (at least 30 mol %, relative to thetotal number of moles of vinyls, vinylidenes, disubstituted vinylenes,and trisubstituted vinylenes), increasing reaction temperature can causea decrease (or at least no increase) in both molecular weight andvinylidene content. Because reaction temperature can be one of the mostubiquitous ways to control product characterization parameters for agiven catalyst system, it can often be a challenge to attain a producthaving both relatively low molecular weight and relatively highvinylidene content in many conventional systems. Thus, in someembodiments of the present disclosure, the combination of thereaction/polymerization/oligomerization conditions with certainmetallocene catalyst systems can advantageously result in bothdecreasing molecular weight and increasing vinylidene content withincreasing reaction temperature, thereby allowing heightened control ofdesired parameters without having to sacrifice one too much to attainthe other. In some embodiments, e.g., by carefully selecting theelements of the metallocene catalyst system, the average activity levelof the catalyst system be can be further advantageously maintained at orabove a sufficiently high level, so as to attain a minimum reasonableyield of oligomeric product, relative to monomeric reactant(s).

Typically, one or more metallocene compounds, one or more activators,and one or more monomers are contacted to produce polymer or oligomer.These catalysts may be supported and, as such, may be useful in theknown slurry, solution, or bulk operating modes conducted in single,series, or parallel reactors. If the catalyst, activator, orco-activator is a soluble compound, the reaction can be carried out in asolution mode. Even if one of the components is not completely solublein the reaction medium or in the feed solution, either at the beginningof the reaction or during or at later stages of the reaction, a solutionor slurry type operation may still be applicable. In any instance, thecatalyst system components, dissolved or suspended insolvents, such astoluene or other conveniently available aromatic solvents, or inaliphatic solvent, or in the feed alpha-olefin stream, can be fed intothe reactor under inert atmosphere (usually nitrogen or argon blanketedatmosphere) to allow the polymerization or oligomerization to takeplace.

The polymerization or oligomerization can be run in a batch mode, whereall the components are added into a reactor and allowed to react to apre-designed degree of conversion, either to partial conversion or fullconversion. Subsequently, the catalyst can be deactivated by anypossible means, such as exposure to air or water, or by addition ofalcohols or solvents containing deactivating agents.

The polymerization or oligomerization can additionally or alternativelybe carried out in a semi-continuous operation, where feeds and catalystsystem components can be continuously and/or simultaneously added to thereactor so as to maintain a constant ratio of catalyst system componentsto feed olefin(s). When all feeds and catalyst system components areadded, the reaction may be allowed to proceed to a pre-determined stage.The reaction can then be discontinued by catalyst deactivation in thesame manner as described for batch operation.

The polymerization or oligomerization can additionally or alternativelybe carried out in a continuous operation, where feeds and catalystsystem components can be continuously and/or simultaneously added to thereactor so to maintain a constant ratio of catalyst system and feedolefins. The reaction product can be continuously withdrawn from thereactor, as in a typical continuous stirred tank reactor (CSTR)operation. The residence times of the reactants can be controlled by apre-determined degree of conversion. The withdrawn product can thentypically be quenched in the separate reactor in a similar manner asother operation. In some embodiments, any of the processes to preparePAOs described herein are continuous processes, which can include a)continuously introducing a feed stream comprising at least 10 mol % ofthe one or more C₆ to C₂₄ alpha-olefins into a reactor, b) continuouslyintroducing the metallocene compound and the activator into the reactor,and c) continuously withdrawing the PAO from the reactor. Additionallyor alternatively, the continuous process can include the step ofmaintaining a partial pressure of hydrogen in the reactor of about 215psi (about 1.5 MPa) or less, based upon the total pressure of thereactor, e.g., about 175 psi (about 1.2 MPa) or less, about 115 psi(about 790 kPa) or less, about 100 psi (about 690 kPa) or less, about 65psi (about 450 kPa) or less, about 50 psi (about 350 kPa) or less, about40 psi (about 280 kPa) or less, about 25 psi (about 170 kPa) or less, orabout 10 psi (about 69 kPa) or less. Additionally or alternatively thehydrogen, if present in the reactor, in the feed, or in both, at aconcentration of about 1000 ppm or less by weight, e.g., about 750 wppmor less, about 500 wppm or less, about 250 wppm or less, about 100 wppmor less, about 50 wppm or less, about 25 wppm or less, about 10 wppm orless, or about 5 wppm or less.

Example reactors can range in size from 2 mL and up. Usually, thereactors are larger than one liter in volume for commercial production.The production facility may have one single reactor, or severalreactors, arranged in series or in parallel or in both to improveproductivity, product properties, and general process efficiency. Thereactors and associated equipment are usually pre-treated to ensureproper reaction rates and catalyst performance. The reaction is usuallyconducted under inert atmosphere, where the catalyst system and feedcomponents may be out of contact with any catalyst deactivator orpoison, e.g., polar oxygen, nitrogen, sulfur, and/or acetyleniccompounds.

One or more reactors in series or in parallel may be used in the presentdisclosure. The metallocene compound, activator and when required,co-activator, may be delivered as a solution or slurry in a solvent orin the alpha-olefin feed stream, either separately to the reactor,activated in-line just prior to the reactor, or pre-activated and pumpedas an activated solution or slurry to the reactor.Polymerizations/oligomerization can be carried out in either singlereactor operation, in which monomer, or several monomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers may be added continuously to a single reactor or in seriesreactor operation, in which the above components can be added to each oftwo or more reactors connected in series. The catalyst system componentscan be added to the first reactor in the series. The catalyst systemcomponent may alternatively be added to both reactors, with onecomponent being added to first reaction and another component to otherreactors. In some embodiments, the metallocene compound can be activatedin the reactor in the presence of olefin. Alternatively, the metallocenecompound (such as a dichloride form of the metallocene compound) may bepre-treated with an alkylaluminum reagent, especiallytriisobutylaluminum, tri-n-hexylaluminum, and/or tri-n-octylaluminum,followed by charging into the reactor containing other catalyst systemcomponent and the feed olefins, or followed by pre-activation with theother catalyst system component to give the fully activated catalyst,which can then be fed into the reactor containing feed olefins. Inanother alternative, the pre-catalyst metallocene can be mixed with theactivator and/or the co-activator, and this activated catalyst can thenbe charged into reactor, together with feed olefin stream containingsome scavenger or co-activator. In another alternative, the whole orpart of the co-activator can be pre-mixed with the feed olefins andcharged into the reactor at the same time as the other catalyst solutioncontaining metallocene and activators and/or co-activator.

The catalyst compositions can be used individually or can be mixed withother known polymerization catalysts to prepare polymer or oligomerblends. Monomer and catalyst selection can allow polymer or oligomerblend preparation under conditions analogous to those using individualcatalysts. Polymers having increased PDI are available from polymersmade with mixed catalyst systems and can thus be achieved. Mixedcatalyst can comprise two or more metallocene compounds and or two ormore activators.

The PAOs described herein can additionally or alternatively be producedin homogeneous solution processes. Generally, this involvespolymerization or oligomerization in a continuous reactor in which thepolymer formed and the starting monomer and catalyst materials suppliedmay be agitated to reduce or avoid concentration or temperaturegradients. Temperature control in the reactor can generally be obtainedby balancing the heat of polymerization and with reactor cooling byreactor jackets or cooling coils or a cooled side-stream of reactant tocool the contents of the reactor, auto refrigeration, pre-chilled feeds,vaporization of liquid medium (diluent, monomers, or solvent) or acombination thereof. Adiabatic reactors with pre-chilled feeds mayadditionally or alternatively be used. The reactor temperature may varywith the catalyst used and the product desired. Higher temperatures cantend to give lower molecular weights, and lower temperatures can tend togive higher molecular weights; however, this is not a fixed rule. Ingeneral, the reactor temperature can vary between about 0° C. and about300° C., e.g., from about 10° C. to about 230° C. or from about 25° C.to about 200° C. Usually, it is important to control the reactiontemperature as pre-determined. In order to produce fluids with narrowpolydispersity., such as to promote the highest possible shearstability, it can be useful to control the reaction temperature toobtain minimum of temperature fluctuation in the reactor or over thecourse of the reaction time. If multiple reactors are used in series orin parallel, it may be useful to keep the temperature constant in apre-determined value, e.g., to minimize any broadening of molecularweight distribution. In order to produce a product with broadermolecular weight distribution, one can adjust the reaction temperatureswing or fluctuation, or, as in series operation, the second reactortemperature may be higher than the first reactor temperature. Inparallel reactor operation, the temperatures of the two reactors may beindependent. More than one type of metallocene catalyst can be used.

The pressure in any reactor used herein can vary from about 0.1atmosphere to about 100 atmospheres (about 1.5 psia to about 1500 psia),e.g., from about 0.5 atm to about 80 atm (from about 7 psia to about1200 psia) or from about 1.0 atm to about 50 atm (from about 15 psia toabout 750 psia). The reaction can be carried out under an atmosphere ofnitrogen or with some hydrogen. Sometimes a small amount of hydrogen maybe added to the reactor to improve catalyst performance. When present,the amount of hydrogen can be kept at such a level to improve catalystproductivity, but not induce too much (such as any significant)hydrogenation of olefins, especially the feed alpha-olefins (thereaction of alpha-olefins into saturated paraffins can be verydetrimental to the efficiency of the process). The amount of hydrogenpartial pressure can be kept low, e.g., less than about 50 psi (about350 kPa), less than about 25 psi (about 170 kPa), less than about 10 psi(about 69 kPa), or less than about 5 psi (about 35 kPa); additionally oralternatively, the concentration of hydrogen in the reactant phase, inthe reactor and/or feed, can be less than about 10,000 ppm (by wt.),e.g., less than about 1000 ppm, less than about 500 ppm, less than about100 ppm, less than about 50 ppm, less than about 25 ppm, or less thanabout 10 ppm.

The reaction time or reactor residence time can depend on the catalystused, the amount of catalyst used, and the desired alpha-olefinconversion level. Different metallocene compounds typically havedifferent activities. Usually, a higher degree of alkyl substitution onthe Cp ring, or bridging can improve catalyst productivity. High amountsof catalyst loading can tend to give higher alpha-olefin conversion atshorter reaction times. However, high amount of catalyst usage can makethe production process uneconomical and difficult to manage the reactionheat or to control the reaction temperature. Therefore, it can be usefulto choose a catalyst with maximum catalyst productivity to minimize theamount of metallocene and activator needed. When the catalyst system isa metallocene plus methylalumoxane, the range of methylalumoxane usedcan be in the range of about 0.1 milligram/gram (mg/g) to about 500 mg/gof alpha-olefin feed, e.g., from about 0.05 mg/g to about 10 mg/g.Furthermore, the molar ratios of the aluminum to metallocene (Al/M molarratio) can range from about 2 to about 4000, e.g., from about 10 toabout 2000, from about 50 to about 1000, or from about 100 to about 500.When the catalyst system is a metallocene plus a Lewis Acid or an ionicpromoter with NCA component, the metallocene use can be in the range ofabout 0.01 microgram/gram (mcg/g) to about 500 mcg/g of metallocenecomponent relative to alpha-olefin feed, e.g., from about 0.1 mcg/g toabout 100 mcg/g, and/or the molar ratio of the NCA activator tometallocene can be in the range from about 0.1 to about 10, e.g., fromabout 0.5 to about 5 or from about 0.5 to about 3. If a co-activator ofalkylaluminum compound is used, the molar ratio of the Al to metallocenecan be in the range from about 1 to about 1000, e.g., from about 2 toabout 500 or from about 4 to about 400.

In some embodiments, the process can have the highest possiblealpha-olefin conversion (close to 100%) of feed alpha-olefin in shortestpossible reaction time. However, in CSTR operation, sometimes it can bebeneficial to run the reaction at an optimum alpha-olefin conversion,which can be less than about 100% alpha-olefin conversion, but can beclose to about 1000. There are also occasions, when partial alpha-olefinconversion can be more desirable, e.g., when a narrow product PDI isdesirable, because partial conversion can avoid a PDI broadening effect.If the reaction is conducted to less than 100% conversion of thealpha-olefin, the unreacted starting material after separation fromother product and solvents/diluents can be simply removed, or may berecycled to increase the total process efficiency. Conversion, alsocalled alpha-olefin conversion, is determined by dividing the amount(grams) of isolated PAO recovered from the polymerization mixture (afterthe polymerization has been stopped) by the amount (grams) ofalpha-olefin introduced into the reactor. (When reported in %,conversion =(grams isolated PAO/grams alpha-olefin used)×100). In someembodiments, the conversion for the polymerization reactions describedherein is about 20% or more, alternatively about 40% or more,alternatively about 60% or more, alternatively about 70% or more,alternatively about 80% or more, alternatively about 90% or more,alternatively about 95% or more. Isolated PAO is the PAO productobtained after solvent, unreacted monomer and other volatiles (such asdimer) have been removed (such as by vacuum flash).

Example residence times for any process described herein can be fromabout 1 minute to about 20 hours, e.g., from about 5 minutes to about 10hours.

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The process can be carried out in acontinuous stirred tank reactor or plug flow reactor, or more than onereactor operated in series or parallel. These reactors may or may nothave internal cooling and the monomer feed may or may not berefrigerated. See the general disclosure of U.S. Pat. No. 5,705,577 forgeneral process conditions.

When a solid supported catalyst is used, a slurrypolymerization/oligomerization process generally operates in the similartemperature, pressure, and residence time range as described previously.In a slurry polymerization or oligomerization, a suspension of solidcatalyst, promoters, monomer and comonomers are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor. The catalyst is then separated from the product by filtration,centrifuge, or settlement. The fluid is then distilled to removesolvent, any unreacted components and light product. A portion or all ofthe solvent and unreacted component or light components can be recycledfor reuse.

If the catalyst used is un-supported or is a solution catalyst, when thereaction is complete or when the product is withdrawn from the reactor(such as in a CSTR), the product may still contain soluble, suspended,or mixed catalyst system components. These components can be deactivatedand/or removed. Any of the usual catalyst deactivation methods oraqueous wash methods can be used to remove the catalyst systemcomponent. Typically, the reaction can be deactivated by addition ofstoichiometric amount or excess of air, moisture, alcohol, isopropanol,etc. The mixture can then be washed with dilute sodium hydroxide or withwater to remove catalyst system components. The residual organic layermay then be subjected to distillation to remove solvent, which canoptionally be recycled for reuse. The distillation can further removeany light reaction product, e.g., from C₁₈ and less.

Polymerization or oligomerization in absence of hydrogen may beadvantageous to provide polymers or oligomers with high degree ofunsaturated double bonds.

In some embodiments, in the process of the present disclosure, due tothe structure features of the metallocene compound, the polymerizationreaction mixture exiting the polymerization reactor can typicallycomprise oligomers including vinylidenes, trisubstituted vinylenes,optionally disubstituted vinylenes, and optionally vinyls, optionallyresidual olefin monomer feed, optionally solvents, and componentsderived from the catalyst system.

The polymerization reaction mixture can then be quenched, e.g., by theaddition of a quenching agent such as water, CO₂, methanol, ethanol,mixtures thereof, and the like. Subsequently, the polymerizationreaction mixture can be separated to remove the residual monomer, whichcan be recycled to the polymerization reactor. Monomer removal can becarried out by means such as flashing under vacuum, distillation, orextraction. The resultant mixture can comprise a first reactor effluentincluding vinylidenes, trisubstituted vinylenes, optionallydisubstituted vinylenes, and optionally vinyls.

Without being bound by theory, it is believed that, a non-coordinatinganion with a large molecular size (e.g., dimethylaniliniumtetrakisperfluoronaphthylborate) can tend to result in higherselectivity toward vinyls and a lower selectivity toward vinylidenes, ascompared to non-coordinating anions with a small molecular size (e.g.,dimethylanilinium tetrakisperfluorophenylborate) when used as theactivator for the same metallocene compound of the present disclosure.

[11] Optionally, hydrogen is absent or present at 1 mol % or less,preferably 0.5 mol % or less in the first polymerization reaction.Optionally no hydrogen is added into the polymerization process.

[12] In an embodiment of the invention, little or no scavenger is usedin the first polymerization to produce the polymer, i.e., scavenger(such as trialkyl aluminum, e.g. tri-n-octylaluminum) is present at zeromol %, alternately the scavenger is present at a molar ratio ofscavenger metal to transition metal of less than 100:1, preferably lessthan 50:1, preferably less than 15:1, preferably less than 10:1.Alternately less than 100 ppm of scavenger is present in the firstpolymerization. Preferably less than 100 ppm of alkylaluminum, such astrialkyl aluminum, is present in the first polymerization reaction.Trialkyl aluminum is typically represented by the formula R₃Al, whereeach R is independently, a C₁ to C₄₀, preferably C₁ to C₂₀ alkyl group,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, docecyl, isomers thereof, and mixtures thereof.[13] In an embodiment, little or no alumoxane (i.e., less than 0.001 wt%) is used in the first polymerization processes described herein. In anembodiment, alumoxane is present at 0.00 mol %, or the alumoxane ispresent at a molar ratio of aluminum to catalyst compound transitionmetal less than 500:1, or less than 300:1, or less than 100:1, or lessthan 1:1.[14] Alternately C₄ olefins (such as isobutylene, butadiene, n-butene)are substantially absent from the PAO and/or the polymerization process.Alternately C₂ to C₄ olefins are substantially absent from the PAO andor the polymerization process (first and or second polymerizations).Alternately isobutylene is substantially absent from the PAO and or thepolymerization process (first and or second polymerizations). Bysubstantially absent is meant that the monomer(s) is/are present in thePAO at 1 wt % or less, preferably at 0.5 wt % or less, preferably at 0wt %. Likewise substantially absent in relation to the polymerizationprocess means that the monomer(s) is/are present in the monomer feed at1 wt % or less, preferably at 0.5 wt % or less, preferably at 0 wt %.[15] Optionally the catalyst productivity is 50,000 grams of PAO productper gram of first catalyst (gPAO/gCat) or more, preferably 55,000gPAO/gCat or more, preferably 60,000 gPAO/gCat or more, preferably100,000 gPAO/gCat or more.[16] Optionally PAO dimer selectivity is 85% or more, preferably 90% ormore, preferably 95% or more, based upon the PAO produced.[17] Optionally the first polymerization temperature is 100° C. or more,preferably 100° C. or more, preferably 120° C. or more.[18] Optionally the first polymerization residence time is 1 hour ormore, preferably 2 hours or more, preferably 3 hours or more, optionallyup to 5 hours.[19] Optionally hydrogen is absent or present at 1 mol % or less in thepolymerization reaction (first and/or second), preferably 0.5 mol % orless in the first and or second polymerization reaction; little or noscavenger is used in the first and or second polymerization to producethe polymer; the catalyst productivity is 50,000 grams of PAO productper gram of catalyst (gPAO/gCat) or more, preferably 55,000 gPAO/gCat ormore, preferably 60,000 gPAO/gCat or more, preferably 100,000 gPAO/gCator more; the PAO dimer selectivity in the first polymerization is 85% ormore, preferably 90% or more, preferably 95% or more, based upon the PAOproduced; and the reactor temperature of the first polymerization is100° C. or more, preferably 100° C. or more, preferably 120° C. or more.[20] Optionally, the PAO produced has an Mn of 350 g/mol or less and thecatalyst has high conversion (e.g., at least 60%, at least 70%, at least80%, at least 90%, based upon the weight of the monomer entering thefirst reactor and the PAO produced).[21] Optionally the catalyst loading is 0.1 gram catalyst per gram ofmonomer or less (gCat/gMon), preferably 0.01 gCat/gMon or less,preferably 0.005 gCat/gMon or less, preferably 0.001 gCat/gMon or less,preferably 0.0001 gCat/gMon or less.[22] Optionally, the PAO produced has an Mn of 350 g/mol or less and thecatalyst has high conversion (e.g., at least 60%, at least 70%, at least80%, at least 90%, based upon the weight of the monomer entering thefirst reactor and the PAO produced), and the catalyst loading is 0.1gram catalyst per gram of monomer or less (gCat/gMon) in the firstreactor, preferably 0.01 gCat/gMon or less, preferably 0.005 gCat/gMonor less, preferably 0.001 gCat/gMon or less, preferably 0.0001 gCat/gMonor less.

Optionally, vinylidene content of the PAO produced is 95% or more,preferably 98% or more, the M_(n) is 350 g/mol or less, preferably 320g/mol or less, preferably 300 g/mol or less, the conversion is at least60%, at least 70%, at least 80%, at least 90%, based upon the weight ofthe monomer entering the first reactor and the PAO produced, the PAOdimer selectivity is at least 60%, at least 70%, at least 80%, at least90%, based upon the weight of the PAO produced in the first reactor, andthe productivity of the continuous process is at least 60,000 g/hour(preferably 70,000 g/hour or more, preferably 100,000 g/hr or more) witha catalyst loading is 0.1 gram catalyst per gram of monomer or less(gCat/gMon) in the first reactor, preferably 0.01 gCat/gMon or less,preferably 0.005 gCat/gMon or less, preferably 0.001 gCat/gMon or less,preferably 0.0001 gCat/gMon or less.

V. Additional Embodiments

The present disclosure provides, among others, the followingembodiments, each of which may be considered as optionally including anyalternate embodiments:

Clause 1. A process to produce a poly alpha-olefin (PAO), comprising:

introducing a first alpha-olefin and a first catalyst system comprisinga metallocene compound into a continuous stirred tank reactor or acontinuous tubular reactor under first reactor conditions, wherein thealpha-olefin is introduced to the reactor at a flow rate of about 100g/hr, to form a first reactor effluent comprising PAO dimer comprisingat least 96 mol % of vinylidene and 4 mol % or less of trisubstitutedvinylene and disubstituted vinylene, based on total moles of vinylidene,trisubstituted vinylene, and disubstituted vinylene; and

introducing the first reactor effluent, a second alpha-olefin and asecond catalyst composition comprising an acid catalyst into a secondreactor under second reactor conditions to form a second reactoreffluent comprising PAO trimer.

Clause 2. The process of Clause 1, wherein the metallocene compound isrepresented by the formula:

wherein:

each of R¹, R², and R³ is independently hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbylgroup, wherein a first one of R¹, R², and R³ is not hydrogen and atleast one of R¹, R², and R³ is hydrogen;

each of R⁴, R⁵, R⁶, and R⁷ is independently hydrogen, a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbylgroup, or one or more of R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷, takentogether with the carbon atoms in the indenyl ring to which they aredirectly connected, collectively form one or more substituted orunsubstituted rings fused to the indenyl ring;

each of R¹, R⁹, R¹⁰, R¹¹, and R¹² is independently a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbyl,silylcarbyl, or germanyl group;

M is a group 3, 4 or 5 transition metal;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched linear, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to 1, 2, or 3.

Clause 3. The process of Clause 1, wherein the metallocene compound isrepresented by the formula:

wherein:

each of R¹, R², and R³ is independently hydrogen or a substituted orunsubstituted linear, branched linear, or cyclic C₁-C₂₀ hydrocarbyl orsilylcarbyl group;

each of R⁴ and R⁷ is independently a substituted or unsubstitutedlinear, branched linear, or cyclic C₁-C₃₀ hydrocarbyl or silylcarbylgroup;

each of R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently a hydrogen, or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl, silylcarbyl, or germanyl group, or optionally at leastthree of R⁸, R⁹, R¹⁰, R¹¹, and R¹² are not hydrogen;

each of R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently hydrogen or asubstituted or unsubstituted linear, branched linear, or cyclic C₁-C₂₀hydrocarbyl or silylcarbyl group;

M is a group 3, 4 or 5 transition metal;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to 1, 2, or 3.

Clause 4. The process of any one of Clauses 1-3, wherein the firstalpha-olefin is a C₆-C₁₆ alpha-olefin.

Clause 5. The process of any one of Clauses 1-4, wherein the secondalpha-olefin is a C₆-C₁₆ alpha-olefin.

Clause 6. The process of any one of Clauses 1-5, wherein the acidcatalyst is a Lewis acid.

Clause 7. The process of any one of Clauses 1-6, wherein the secondreactor conditions comprise an acid catalyst loading of from about 5mmolCat/100 gLAO to about 15 mmolCat/100 gLAO.

Clause 8. The process of any one of Clauses 1-7, wherein the secondreactor conditions comprise a temperature of from about 10° C. to about40° C.

Clause 9. The process of any one of Clauses 1-8, wherein the acidcatalyst is BF₃.

Clause 10. The process of any one of Clauses 1-9, wherein the amount ofPAO trimer in the second reactor effluent is 75 wt % or more, based on atotal weight of PAO dimer, PAO trimer, and higher oligomers, where thehigher oligomers are oligomers that have degree of polymerization of 4or more, of alpha-olefin in the second reactor effluent.Clause 11. The process of Clause 10, wherein the second reactor effluentcomprises, 75 wt % or more of PAO trimer, 9 wt % or less of PAO dimer,and 16 wt % or less of higher oligomers of alpha-olefin., based on atotal weight of PAO dimer, PAO trimer, and higher oligomers ofalpha-olefin in the second reactor effluent.Clause 12. The process of any one of Clauses 1-11, wherein the amount ofPAO trimer in the second reactor effluent is greater than 80 wt %, basedon a total weight of PAO dimer, PAO trimer, and higher oligomers ofalpha-olefin in the second reactor effluent.Clause 13. The process of any one of Clauses 1-12, wherein the amount ofvinylidene in the PAO dimer in the first reactor effluent is about 96mol % or more, based on total moles of vinylidene, disubstitutedvinylene, and trisubstituted vinylene in the PAO dimer in the firstreactor effluent.Clause 14. The process of Clause 13, wherein the PAO dimer in the firstreactor effluent further comprises, based on the total moles (100 mol %)of vinylidene, disubstituted vinylene, and trisubstituted vinylene inthe PAO dimer in the first reactor effluent:

up to 4 mol % of trisubstituted vinylene,

up to 4 mol % of disubstituted vinylene, or

up to 4 mol % of trisubstituted vinylene and disubstituted vinylene.

Clause 15. The process of any one of Clauses 1-14, wherein the PAO dimerin the first reactor effluent comprises, based on total moles (100 mol%) of vinylidene, disubstituted vinylene, and trisubstituted vinylene inthe PAO dimer in the first reactor effluent:

98 mol % or more vinylidene, and up to 2 mol % of trisubstitutedvinylene, and/or disubstituted vinylene.

Clause 16. The process of any one of Clauses 1-15, wherein the PAO dimerin the first reactor effluent further comprises, based on the totalmoles (100 mol %) of vinylidene, disubstituted vinylene, andtrisubstituted vinylene in the PAO dimer in the first reactor effluent:

98 mol % or more vinylidene, and

up to 1 mol % trisubstituted vinylene,

up to 1 mol % disubstituted vinylene, or

up to 1 mol % trisubstituted vinylene and disubstituted vinylene.

Clause 17. The process of any one of Clauses 1-16, wherein the PAO dimerin the first reactor effluent further comprises, based on the totalmoles (100 mol %) of vinylidene, disubstituted vinylene, andtrisubstituted vinylene in the PAO dimer in the first reactor effluent:

98 mol % or more vinylidene, and

up to 0.5 mol % trisubstituted vinylene,

up to 0.5 mol % disubstituted vinylene, or

up to 0.5 mol % trisubstituted vinylene and disubstituted vinylene.

Clause 18. The process of any one of Clauses 1-17, wherein the activatorcomprises one or more of:

N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,

N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,

triphenylcarbonium tetrakis(perfluorophenyl)borate,

triphenylcarbonium tetrakis(perfluoronaphthyl)borate,

N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,

N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate alumoxane,modified alumoxane, and aluminum alkyl.

Clause 19. The process of any one of Clauses 1-18, wherein the secondcatalyst composition further comprises an alcohol and an alkyl acetate.

Clause 20. The process of any one of Clauses 1-19, wherein themetallocene compound is selected from the group consisting of:

or a combination thereof.Clause 21. The process of any one of Clauses 1-20, wherein the secondreactor conditions include a second reactor temperature of less than 60°C. and an acid catalyst composition loading of less than 30 mmol per 100g of second alpha-olefin.Clause 22. The process of any one of Clauses 1-21, wherein the PAOtrimer has a number average molecular weight (Mn) of 300 or less, inaccordance with ¹H nuclear magnetic resonance spectroscopy.Clause 23. The process of any of Clauses 1 to 22, further comprisingfunctionalizing the PAO trimer with a reactant to form a functionalizedPAO product.Clause 24. The process of any of Clauses 1 to 23, further comprisinghydrogenating the product, PAO trimer, or functionalized PAO product toform a hydrogenated PAO product.Clause 25. A lubricant comprising the PAO dimer, PAO trimer,functionalized PAO product, or hydrogenated PAO product produced in anyof Clauses 1 to 24.Clause 26. A fuel comprising the PAO dimer, PAO trimer, functionalizedPAO product, or hydrogenated PAO product produced in any of Clauses 1 to24.Clause 27. A driveline or electric vehicle fluid comprising the PAOdimer, PAO trimer, functionalized PAO product, or hydrogenated PAOproduct produced in any of Clauses 1 to 24.Clause 28. An engine oil comprising the PAO dimer, PAO trimer,functionalized PAO product, or hydrogenated PAO product produced in anyof Clauses 1 to 24.Clause 29. A gear oil comprising the PAO dimer, PAO trimer,functionalized PAO product, or hydrogenated PAO product produced in anyof Clauses 1 to 24.Clause 30. A compressor oil comprising the PAO dimer, PAO trimer,functionalized PAO product, or hydrogenated PAO product produced in anyof Clauses 1 to 24.Clause 31. The process of Clauses 1 to 24 wherein the process has aconversion of at least 60%, based upon the weight of the monomerentering the reactor and the PAO produced and a selectivity for dimer ofat least 85 wt %, based upon the PAO produced; and the metallocenecompound is represented by formula (Z):

wherein:

each R¹, R², and R³ is, independently, hydrogen or a substituted orunsubstituted linear, branched (such as branched linear), or cyclicC₁-C₂₀, preferably C₁-C₈, hydrocarbyl group, wherein one of R¹, R², andR³ is a substituted or unsubstituted linear, branched (such as branchedlinear), or cyclic C₁-C₂₀, preferably C₁-C₈, hydrocarbyl group, andeither (i) two of R¹, R², and R³ are each a hydrogen, or (ii) one of R¹,R², and R³ is a hydrogen or a substituted or unsubstituted linear,branched (such as branched linear), or cyclic C₁-C₂₀, preferably C₁-C₈,hydrocarbyl group, and one of R¹, R², and R³, taken together with R¹⁶,is a bridging group connecting the first and second cyclopentadienylrings;

R⁴ and R⁵ are each independently a substituted or unsubstituted linear,branched (such as branched linear), or cyclic C₁-C₃₀ hydrocarbyl group,or R⁴ and R⁵, taken together with the carbon atoms in the firstcyclopentadienyl ring to which they are directly connected, collectivelyform one or more substituted or unsubstituted rings annelated to thefirst cyclopentadienyl ring;

R¹², R¹³, R¹⁴, and R¹⁵ are each independently a hydrogen, or asubstituted or unsubstituted linear, branched (such as branched linear),or cyclic C₁-C₂₀, preferably C₁-C₈, hydrocarbyl group; and

R¹⁶ is a hydrogen, a substituted or unsubstituted linear, branched (suchas branched linear), or cyclic C₁-C₂₀, preferably C₁-C₅, hydrocarbylgroup, substituted silyl or substituted germanyl group, or, takentogether with one of R¹, R², and R³, is a bridging group connecting thefirst and second cyclopentadienyl rings, optionally at least three ofR², R¹³, R¹⁴, R¹⁵, and R¹⁶ are not hydrogen, optionally two or more ofR¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ moieties may together form a fused ring orring system, provided that the fused ring or ring system is notunsaturated when R¹ is bridged to R¹⁶, and where R² is not Me when R¹ orR³ is bridged to R¹⁶;

M is a transition metal having an integer valency of v;

each X is independently a halogen, a hydride, an amide, an alkoxide, asulfide, a phosphide, a diene, an amine, a phosphine, an ether, or aC₁-C₂₀ substituted or unsubstituted linear, branched, or cyclichydrocarbyl group, or optionally two or more X moieties may togetherform a fused ring or ring system; and

m is an integer equal to v-2.

Clause 32. The process of Clause 31, wherein one of R¹, R², and R³ is asubstituted or unsubstituted linear, branched (such as branched linear),or cyclic C₁-C₆ hydrocarbyl group, and two of R¹, R², and R³ are each ahydrogen.

Clause 33. The process of Clause 31, wherein one of R¹ and R³ is asubstituted or unsubstituted linear, branched (such as branched linear),or cyclic C₁-C₆ hydrocarbyl group, R² is a hydrogen, and one of R¹ andR³ is a substituted or unsubstituted linear, branched (such as branchedlinear), or cyclic C₁-C₆ hydrocarbyl group, or, taken together with R¹⁶,is a bridging group connecting the first and second cyclopentadienylrings.Clause 34. The process of Clause 33, wherein the bridging groupcomprises:

where each G4, the same or different at each occurrence, isindependently carbon, silicon, or germanium, and R¹⁷, the same ordifferent at each occurrence, is each independently a C₁-C₂₀, preferablyC₁-C₈, substituted or unsubstituted linear, branched, or cyclichydrocarbyl group.Clause 35. The process of any one of the preceding Clauses 31 to 34,wherein each X is independently a halogen or a substituted orunsubstituted linear, branched, or cyclic C₁-C₆ hydrocarbyl group; Mcomprises Zr or Hf and m is 2.

Clauses 36. The process of any one of the preceding Clauses 31 to 35,wherein M is Zr, m is 2 and each X is independently a methyl, an ethyl,a propyl, a butyl, a phenyl, a benzyl, a chloride, a bromide, or aniodide.

Clauses 37. The process of Clause 31 wherein the a polymerizationreactor is a continuous stirred tank reactor or a continuous tubularreactor, the alpha-olefin is introduced to the reactor at a flow rate ofat least 100,000 g/hr, the polymerization residence time is from 2 to 5hours, and the polymerization temperature is 120° C. or more.

Clause 38. The process of Clause 37 where the vinylidene content of thePAO produced is 95% or more based on total moles of vinylidene,disubstituted vinylene, and trisubstituted vinylene in the PAO product,the Mn of the PAO product is 350 g/mol or less, the conversion is atleast 60%, at least 70%, at least 80%, at least 90%, based upon theweight of the monomer entering the reactor and the PAO produced, the PAOdimer selectivity is at least 60%, based upon the weight of the PAOproduced, and the productivity of the continuous process is at least60,000 g/hour with a catalyst loading of 0.1 gram catalyst per gram ofmonomer or less.

VI. Characterization

For the characterization, proton NMR (¹H-NMR) was used to determine themol % of the unsaturated species. Specifically, an NMR instrument of 500MHz is run under the following conditions: a 30° flip angle RF pulse, 8scans, with a relaxation delay of ˜5 s between pulses; sample (60-100mg) dissolved in CDCl₃ (deuterated chloroform) in a 5 mm NMR tube; andsignal collection temperature at about 25° C. The following approach istaken in determining the concentrations of the various olefins among allof the olefins from an NMR spectrum. First, peaks corresponding todifferent types of hydrogen atoms in vinyls (TI), vinylidenes (T2),disubstituted vinylenes (T3), and trisubstituted vinylenes (T4) areidentified at the peak regions in Table A. Second, areas of each of theabove peaks (A1, A2, A3, and A4, respectively) are then integrated.Third, quantities of each type of olefins (Q1, Q2, Q3, and Q4,respectively) in moles are calculated (as A1/2, A2/2, A3/2, and A4,respectively). Fourth, the total quantity of all olefins (Qt) in molesis calculated as the sum total of all four types (Qt=Q1+Q2+Q3+Q4).Finally, the molar concentrations (C₁, C₂, C₃, and C₄, respectively, inmol %) of each type of olefin, on the basis of the total molar quantityof all of the olefins, is then calculated (in each case, Ci=100*Qi/Qt).

TABLE A Hydrogen Atoms Peak Number of Concentration Type Olefin RegionPeak Hydrogen Quantity of of Olefin No. Structure (ppm) Area AtomsOlefin (mol) (mol %) T1 CH₂═CH—R¹ 4.95-5.10 A1 2 Q1 = A1/2 C1 T2CH₂═CR¹R² 4.65-4.84 A2 2 Q2 = A2/2 C2 T3 CHR¹═CHR² 5.31-5.55 A3 2 Q3 =A3/2 C3 T4 CR¹R²═CH R³ 5.11-5.30 A4 1 Q4 = A4 C4

Gas chromatography (GC) was used to determine the composition of thesynthesized oligomers by molecular weight. The gas chromatograph is a HPmodel equipped with a 15 meter dimethyl siloxane and flame ionizationdetector. A ˜0.04 g sample was diluted in methylene chloride solvent, anonane internal standard was added, and the mixture injected into thecolumn. The starting temperature was about 40° C., held for about 1minute, program-heated at about 15° C. per minute to about 250° C. andheld for about 2 minutes. The sample was then heated at a rate of about25° C. per minute to about 360° C. and held for about 17.3 minutes. Theconversion, olefin isomerization, and oligomer distribution can bedetermined by the GC method.

VII. Examples VII. A. Examples—Metallocene Dimer Selective Process

All catalyst syntheses were carried out in an N₂ purged dry box usingstandard air sensitive procedures. Celite (Sigma-Aldrich) and 3 Åmolecular sieves (Sigma-Aldrich or Acros) were dried in a vacuum oven at250° C. for 3 days. Solvents were purged with N² and dried and storedover 3 Å molecular sieves. NMR solvents were dried and stored over 3 Åmolecular sieves. MeMgI (3 M in Et₂O, Sigma-Aldrich), CH₃I(Sigma-Aldrich), isoButyl bromide (Sigma-Aldrich), nhexyl bromide(Sigma-Aldrich), nbutyl bromide (Sigma-Aldrich),1,2,3,5-tetrahydro-s-indacene (GLSyntech) were used as received.Pentamethylcyclopentadienylhafnium trichloride (Me₅CpHfCl₃) was eitherpurchased from Strem Chemicals or synthesized in a manner analogous tothat described in Journal of Organometallic Chemistry, 1988, v. 340,37-40.

Pentamethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)HfMe₂(Catalyst I.A)

1-Methyl-1,5,6,7-tetrahydro-s-indacenyl Lithium:1,5,6,7-tetrahydro-s-indacenyl lithium was synthesized in a manneranalogous to that described in U.S. Ser. No. 16/270,085.

MeI (6.74 g, 47.5 mmol) was slowly added to1,5,6,7-tetrahydro-s-indacenyl Lithium (7.0 g, 43.2 mmol) in Et₂O (100ml) and THF (20 ml). The reaction stirred for 4 hours. All solvents werethen removed by a stream of nitrogen and the crude product wasreslurried into pentane for 15 minutes. The solid was removed byfiltration on celite. The solid was washed by pentane. All solvents werethen removed in vacuo and 1-methyl-1,5,6,7-tetrahydro-s-indacene wasisolated as a clear oil (6.95 g, 41.0 mmol), which was then dissolvedinto Et₂O (100 ml). nBuLi (3.7 ml, 11M) was then slowly added andstirred for 1 hour. Then all Et₂O was removed in vacuo and then pentanewas added to the solution and the mixture was stirred for additional 10minutes and then filtered to collect the product as a white solid (6.97g).

1-methyl (1,5,6,7-tetrahydro-s-indacenyl) lithium (0.3 g, 1.6 mmol) wasmixed with CpMe₅HfCl₃ (0.7 g, 1.1 mmol) in Et₂O (15 ml) and stir itovernight. Et₂O was then removed by a stream of nitrogen and the crudeproduct was re-slurried into pentane for 15 minutes and was cooled under−35° C. The product was isolated by filtration as a mixture of LiCl andwas used for the next step with no further purification. The crudehafnium dichloride (0.78 g, 1.4 mmol) was slurried into toluene (20 ml)and MeMgI (0.94 ml, 3 M in Et₂O) was then added and the reaction wasstirred at 70° C. for 16 hours. The reaction was cooled to roomtemperature and 1,4-dioxane was added. The mixture was stirred for 15minutes, and the solids were removed by filtration on CELITE and washedby Et₂O. Volatiles were then removed under vacuo. Final product(C₂₅H₃₄Hf) was isolated as a solid (0.4 g), which was analyzed by ¹H NMR(CD₂Cl₂, 400 MHz): δ 7.45-7.33 (m, 1H), 7.02-6.92 (m, 1H), 5.32 (dd,J=2.9, 0.9 Hz, 1H), 5.27 (dd, J=2.8, 0.6 Hz, 1H), 2.99-2.86 (m, 4H),2.19 (s, 3H), 2.11-1.99 (m, 2H), 1.88 (s, 15H), −1.08 (s, 3H), −2.12 (s,3H).

Pentamethylcyclopentadienyl (1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)HfMe₂ (Catalyst I.B)

1-isoButyl-1,5,6,7-tetrahydro-s-indacenyl Lithium: isoButyl bromide(1.69 g, 12 mmol) was added to 1,5,6,7-tetrahydro-s-indacenylLithium(2.0 g, 12 mmol) in THF (100 ml). The reaction stirred for 16hours. THF was then removed by a stream of nitrogen, and the crudeproduct was reslurried into pentane for 15 minutes. The solid wasremoved by filtration on celite. The solid was washed by pentane. Allsolvents were then removed in vacuo and1-isoButyl-1,5,6,7-tetrahydro-s-indacene was isolated as a clear oil(2.54 g, 12 mmol), which was dissolved into Et₂O (50 ml). nBuLi (1.1 ml,11M) was then slowly added and stirred for 1 hour. Then all Et₂O wasremoved in vacuo and then pentane was added to the solution and stirredfor additional 10 minutes and filtered to collect the product as a whitesolid (2.5 g).

1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl lithium (0.27 g, 1.2 mmol) wasmixed with CpMe₅HfCl₃ (0.52 g, 1.2 mmol) in Et₂O (20 ml) and stirredovernight. Et₂O was then removed by a stream of nitrogen and the crudeproduct was reslurried into pentane for 15 minutes. The mixture wascooled at −35° C. for 1 hour. The product was isolated by filtration asa mixture of LiCl and was used for the next step with no furtherpurification. The crude hafnium dichloride (0.68 g, 1.1 mmol) wasslurried into toluene (20 ml) and MeMgI (0.71 ml, 3 M in Et₂O) was thenadded and the reaction was stirred at 70° C. for 16 hours. The reactionwas cooled to room temperature and 1,4-dioxane (0.38 ml) was added. Themixture was stirred for 15 minutes and solids were removed by filtrationon CELITE and washed by Et₂O. Volatiles were then removed under vacuo.The product slowly became a solid, to which was added 0.5 ml of pentane.This was swirled and cooled at −35° C. for 3 hours, and pentane waspipetted away. Final product (C₂₈H₄₀Hf) was isolated as a solid (0.4 g),which was analyzed by 1H NMR (CD2Cl2, 400 MHz): δ 7.38 (s, 1H), 6.97 (d,J=1.4 Hz, 1H), 5.34 (dd, J=2.9, 0.8 Hz, 1H), 5.27 (d, J=2.9 Hz, 1H),2.99-2.88 (m, 4H), 2.80 (dd, J=13.5, 5.8 Hz, 1H), 2.04 (p, J=7.3 Hz,2H), 1.93-1.79 (m, 17H), 0.93 (d, J=6.5 Hz, 3H), 0.85 (d, J=6.4 Hz, 3H),−1.08 (s, 2H), −2.14 (s, 3H).

Dimethylsilyl(tetramethylcyclopentadienyl) 1-isobutylindenyl) HafniumDimethyl (Catalyst I.C)

Indenyl Lithium: To a solution of indene (10 g, 86.1 mmol) was slowlyadded 1M nBuLi (7.9 ml, 86.9 mmol) and stirred for 1 hour. Then all Et₂Owas removed under vacuo and then add pentane into the solution and letit stir for additional 10 minutes then filter to collect the product asa white solid (10.0 g).

Indenyl lithium (6.55 g, 54 mmol) was mixed with isobutyl Bromide (7.35,54 mmol) in THF (30 ml)/Et₂O (100 ml) and stirred at room temperaturefor 16 hours. All solvents were removed under vacuo, and the crudeproduct was reslurried into pentane. All solids were removed byfiltration on Celite. Then all solvents were removed by a stream ofnitrogen. The crude product was isolated as a clear oil. To the solutionof the oil (7.9 g, 46 mmol) in Et₂O (50 ml) was slowly added 11M nBuLi(4.17 ml). The reaction stirred at room temperature for 30 minutes. MostEt₂O was removed by a stream of nitrogen. Then pentane was added and themixture was stirred for 10 minutes. The lithiated product was collectedby filtration as a solid (7.85 g) and was used with no furtherpurification. 5.9 g of the solid was then mixed with CpMe₅HfCl₃ (13.07g, 33 mmol) in Et₂O (100 ml) and was stirred overnight. Most Et₂O wasthen removed by a stream of nitrogen and pentane was added, thenfiltered to collect the crude product, which was used for the next stepwith no further purification. The crude Hafnium dichloride (14.65 g.25.5 mmol) was slurried into toluene (50 ml) and MeMgI (16.3 ml, 3 M inEt₂O) was then added and the reaction was stirred at 70° C. for 16hours. The reaction was cooled to room temperature and 1,4-dioxane wasadded. The mixture was stirred for 15 minutes and solids were removed byfiltration on Celite and was washed by Et₂O. All volatiles were thenremoved under vacuo. 3 ml of pentane was added to help the productsolidify. Pure product (C₂₅H₃₆Hf) was isolated as a solid (11.0 g),which was analyzed by ¹H NMR (CDCl₃, 400 MHz): δ 7.63-7.57 (m, 1H),7.21-7.10 (m, 3H), 5.43 (d, J=2.9, 1H), 5.36 (d, J=2.9 Hz, 1H), 2.85(dd, J=13.8, 6.0 Hz, 1H), 2.11-1.80 (m, 17H), 0.94 (d, J=6.5 Hz, 3H),0.87 (d, J=6.5 Hz, 3H), −1.03 (s, 3H), −2.09 (s, 3H).

Synthesis of (Pentamethylcyclopentadienyl)(1-nHexylindenyl) HafniumDimethyl (21)

Indenyl lithium (0.90 g, 7 mmol) was mixed with n-hexyl bromide (1.32 g,7 mmol) in THF (20 ml) and stirred at room temperature for 16 hours. Allsolvents were removed in vacuo, and the crude product was reslurriedinto pentane. All solids were removed by filtration on Celite. Then allsolvents were removed by a stream of nitrogen. The crude product wasisolated as a clear oil. To the solution of the oil (1.52 g, 7 mmol) inEt₂O (20 ml) was slowly added 11M nBuLi (0.65 ml). The reaction stirredat room temperature for 30 minutes. All Et₂O was removed by a stream ofnitrogen. Then pentane was added and the mixture was stirred for 10minutes and then placed under −35° C. for 30 minutes. The lithiatedproduct was collected by filtration as a solid (1.12 g), which was thenmixed with CpMe₅HfCl₃ (2.11 g, 5 mmol) in Et₂O (15 ml) and was stirredovernight. Most Et₂O was then removed by a stream of nitrogen andpentane was added and then filtered to collect the crude product, whichwas used for the next step with no further purification. The crudeHafnium dichloride (2.15 g, 3 mmol) was slurried into toluene (20 ml)and MeMgI (2.3 ml, 3 M in Et₂O) was then added and the reaction wasstirred at 70° C. for 16 hours. The reaction was cooled to roomtemperature and 1,4-dioxane was added. The mixture was stirred for 15minutes and solids were removed by filtration on Celite and was washedby Et₂O. All volatiles were then removed in vacuo. 1 ml of pentane wasadded to help the product solidify. Pure product (C₂₇H₄₀Hf) was isolatedas a solid (1.6 g), which was analyzed by ¹H NMR (CD₂Cl₂, 400 MHz): δ7.66-7.59 (m, 1H), 7.24-7.11 (m, 3H), 5.48 (dd, J=2.9, 0.8 Hz, 1H), 5.44(d, J=2.9 Hz, 1H), 2.91 (ddd, J=14.8, 9.3, 5.6 Hz, 1H), 2.33 (ddd,J=14.5, 9.6, 6.0 Hz, 1H), 1.92 (s, 15H), 1.77-1.59 (m, 1H), 1.57-1.15(m, 7H), 1.00-0.80 (m, 3H), −1.03 (s, 3H), −2.11 (s, 3H).

Synthesis of (Pentamethylcyclopentadienyl)(1-nButylindenyl) HafniumDimethyl (22)

Indenyl lithium (0.80 g, 7 mmol) was mixed with n-butyl bromide (0.90 g,7 mmol) in THF (20 ml) and stir at room temperature for 16 hours. Allsolvents were removed under vacuo, and the crude product was reslurriedinto pentane. All solids were removed by filtration on Celite. Then allsolvents were removed by a stream of nitrogen. The crude product wasisolated as a clear oil. To the solution of the oil (1.04 g, 6 mmol) inEt₂O (20 ml) was slowly added 11M nBuLi (0.55 ml). Let the reaction stirat room temperature for 30 minutes. All Et₂O was removed by a stream ofnitrogen. Then pentane was added and the mixture was stirred for 10minutes. The lithiated product was collected by filtration as a solid(1.04 g). 0.5 g of the solid was then mixed with CpMe₅HfCl₃ (1.16 g, 3mmol) in Et₂O (15 ml) and was stirred overnight. Most Et₂O was thenremoved by a stream of nitrogen and pentane was added. Filter to collectthe crude product, which was used for the next step with no furtherpurification. The crude Hafnium dichloride (0.88 g, 1 mmol) was slurriedinto toluene (20 ml) and MeMgI (1 ml, 3 M in Et₂O) was then added andthe reaction was stirred at 70° C. for 16 hours. The reaction was cooledto room temperature and 1,4 dioxane was added. The mixture was stirredfor 15 minutes and solids were removed by filtration on Celite and waswashed by Et₂O. All volatiles were then removed under vacuo. 1 ml ofpentane was added to help the product solidify. Pure product (C₂₅H₃₆Hf)was isolated as a solid (0.7 g), which was analyzed by ¹H NMR (CD₂Cl₂,400 MHz): δ 7.64-7.56 (m, 1H), 7.22-7.09 (m, 3H), 5.45 (dd, J=2.9, 0.8Hz, 1H), 5.41 (d, J=2.9 Hz, 1H), 2.95-2.82 (m, 1H), 2.37-2.24 (m, 1H),1.89 (s, 15H), 1.72-1.56 (m, 1H), 1.53-1.25 (m, 3H), 0.93 (t, J=7.3 Hz,3H), −1.06 (s, 3H), −2.14 (s, 3H).

Example I.1 (Using Catalyst I.A)

An about 97% pure 1-decene was fed through an adsorbent column filledwith alumina adsorbent to a stainless steel Parr vessel where it wassparged with nitrogen for 1 hour to obtain a purified feed. The catalystwas Catalyst I.A. A catalyst solution including purified toluene, TNOA,and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafterreferred to as “Activator 1”) was prepared per the following recipebased on 1 gram of Catalyst I.A: Catalyst I.A (1 g), purified toluene(394 g), TNOA (1 g), Activator 1 (1.6 g). The olefin feedstream wasadded at a rate of about 2,080 grams per hour to a 2 gallon stainlesssteel Parr reactor held at about 120° C. for oligomerization. The1-decene and catalyst solution were fed into the reactor at a ratio ofabout 64,200 grams of LAO per gram of catalyst. The residence time inthe reactor was about 2.9 hours. The reactor was run at liquid fullconditions, with no addition of any gas. When the system reachedsteady-state, a reactor effluent was collected and quenched by additionof deionized water. BH-40 was slurried into the reactor effluent at 0.2wt % and the material taken through a vacuum filtration. The conversion,oligomer distribution, and LAO isomerization was determined by GC. Thedimer was then isolated by vacuum distillation. The mole percentage ofeach type of olefin in the distilled intermediate PAO dimer wasdetermined by proton NMR.

Example I.2 (Using Catalyst I.A)

Similar to Example I.1 except about 0.66 grams of TNOA was added to thecatalyst solution, the oligomerization temperature used was about 140°C., and Catalyst I.A was used at a ratio of about 68,100 g LAO/gCat.

Example I.3 (Using Catalyst I.A)

Similar to Example I.1 except the oligomerization temperature used wasabout 130° C., and Catalyst I.A was used at a ratio of about 65,200 gLAO/gCat.

Example I.4 (Using Catalyst I.A)

Similar to Example I.1 except about 0.75 gram of TNOA was added to thecatalyst solution, the oligomerization temperature used was about 140°C., and Catalyst I.A was used at a ratio of about 72,500 g LAO/gCat.

Example I.5 (Using Catalyst I.A)

Similar to Example I.1 except no TNOA was added to the catalystsolution, the oligomerization temperature used was about 140° C., andCatalyst I.A was used at a ratio of about 74,200 g LAO/gCat.

Example I.6 (Using Catalyst I.B)

Similar to Example I.1 except 0.75 g of TNOA was added to the catalystsolution, 1.5 g of Activator I was added to the catalyst solutionrecipe, the oligomerization temperature used was about 135° C., andCatalyst I.A was used at a ratio of about 71,400 g LAO/gCat.

Example I.7 (Using Catalyst I.B)

Similar to Example I.1 except about 0.75 grams of TNOA was added to thecatalyst solution, the oligomerization temperature used was about 140°C., about 1.5 grams of Activator 1 was added to the catalyst solutionrecipe, and Catalyst I.B was used at a ratio of about 72,100 g LAO/gCat.

Example I.8 (Using Catalyst I.B)

Similar to Example I.1 except no TNOA was added to the catalystsolution, the oligomerization temperature used was about 140° C., about1.5 grams of Activator 1 was added to the catalyst solution recipe, andCatalyst I.B was used at a ratio of about 80,300 g LAO/gCat.

Example I.9 (Using Catalyst I.B)

Similar to Example I.1 except the oligomerization temperature used wasabout 148.5° C., about 1.5 grams of Activator 1 was added to thecatalyst solution recipe, and Catalyst I.B was used at a ratio of about67,700 g LAO/gCat.

Example I.10 (Using Catalyst I.B)

Similar to Example I.1 except 50 ppmw of TNOA was additionally addedin-line with the 1-decene prior to addition to the oligomerizationreactor, the oligomerization temperature used was about 130° C., about1.5 grams of Activator 1 was added to the catalyst solution recipe, andCatalyst I.B was used at a ratio of about 82,300 g LAO/gCat.

Example I.11 (Using Catalyst I.B)

Similar to Example I.1 except 50 ppmw of TNOA was additionally addedin-line with the 1-decene prior to addition to the oligomerizationreactor, the oligomerization temperature used was about 105° C., about1.5 grams of Activator 1 was added to the catalyst solution recipe, andCatalyst I.B was used at a ratio of about 82,600 g LAO/gCat.

Example I.12 (Using Catalyst I.B)

Similar to Example I.1 except the oligomerization temperature used wasabout 148° C., about 1.5 grams of Activator I was added to the catalystsolution recipe, and Catalyst I.B was used at a ratio of about 70,000 gLAO/gCat.

Example I.13 (Using Catalyst I.C)

Similar to Example I.1 except 0.87 g of TNOA was added to the catalystsolution, 1.8 grams of Activator 1 was added to the catalyst solutionrecipe, and Catalyst I.C was used at a ratio of about 87,200 g LAO/gCat.

Example I.14 (Using Catalyst I.C)

Similar to Example I.1, except the temperature used was 110° C., 0.87 gof TNOA was added to the catalyst solution, 1.8 grams of Activator 1 wasadded to the catalyst solution recipe, and Catalyst I.C was used at aratio of about 87,200 g LAO/gCat.

Example C.Ex.1.1 (Using Catalyst C.Cat. A)

Similar to Example I.1 except that about the 1-decene flowrate was 3,000g/hr so that the reactor residence time was about 2 hours, 250 ppmw ofTNOA was additionally added in-line with the 1-decene prior to additionto the oligomerization reactor, about 6 grams of TNOA was added to thecatalyst batch recipe, about 1.9 grams of Activator I was added to thecatalyst solution recipe, and Catalyst C.Cat. A was added at a ratio ofabout 33,500 g LAO/gCat.

Three of the Hf-based metallocene catalysts that demonstrate the dimerselective process to produce olefins having very high vinylidene contentand very low vinylene content are shown in Scheme 1. The comparativecatalyst, C.Cat. A, is also shown in Scheme 1:

FIG. 3 (Catalyst I.A) and FIG. 4 (Catalyst I.B) are plots of theoligomer distributions (dimer, trimer, and heavies) produced by themetallocene dimer selective process at various temperatures. BothCatalyst I.A and Catalyst I.B produce dimer (C₂₀) selectivity of about87% or more with very low trimer and heavies content (higher oligomersof alpha olefin).

Tables 2 and 3 show various characteristics of the oligomerization forinventive Examples such as Dimer Selectivity, distributions of theolefins in terms of mole percentages of each type as determined by ¹HNMR, the catalyst productivity, the catalyst activity, the LAOconversion, and LAO isomerization.

TABLE 2 Trisubstituted Cat. Cat Activity LAO LAO Dimer VinylideneVinylene Vinylene Productivity (g PAO/sec Conversion IsomerizationSample Cat. Selectivity (mol %) (mol %) (mol %) (gPAO/gCat) mol cat) (wt%) (wt %) Ex. I.1 I.A 78.9 96.4 3.3 0.3 52,300 2,480 81 1.8 Ex. I.2 I.A90.1 94.9 4.8 0.3 58,500 2,780 86 2.6 Ex. I.3 I.A 88.7 N/D N/D N/D58,500 2,780 90 1.9 Ex. I.4 I.A 89.6 N/D N/D N/D 60,100 2,860 83 2.2 Ex.I.5 I.A 85.8 N/D N/D N/D 49,200 2,340 66 2.0 Ex. I.6 I.B 91.2 97.9 2.00.1 60,700 3,000 85 2.2 Ex. I.7 I.B 92.6 N/D N/D N/D 62,500 3,090 87 2.5Ex. I.8 I.B 81.7 N/D N/D N/D 23,800 1,170 30 1.6 Ex. I.9 I.B 93.3 N/DN/D N/D 55,700 2,750 82 2.5 Ex. I.B 79.7 97.8 2.0 0.2 61,000 3,010 741.9 I.10 Ex. I.B 59.3 N/D N/D N/D 52,700 2,600 64 1.5 I.11 Ex. I.B 92.2N/D N/D N/D 57,100 2,820 82 2.6 I.12 Ex. I.C 91.9 96.8 3.0 0.2 68,2002,980 78 2.6 I.13 Ex. I.C 88.1 N/D N/D N/D 73,500 3,200 84 2.4 I.14 C.Ex. C.Cat A 43.6 48.8 41.1  10.0  31,800 1,830 95 2.7 I.1

TABLE 3 Cat Activity Cat. (g LAO LAO Productivity PAO/sec ConversionIsomerization Sample Cat. (gPAO/gCat) mol cat) (wt %) (wt %) Ex. I.1 I.A52,300 2,480 81 1.8 Ex. I.2 I.A 58,500 2,780 86 2.6 Ex. I.3 I.A 58,5002,780 90 1.9 Ex. I.4 I.A 60,100 2,860 83 2.2 Ex. I.5 I.A 49,200 2,340 662.0 Ex. I.6 I.B 60,700 3,000 85 2.2 Ex. I.7 I.B 62,500 3,090 87 2.5 Ex.I.8 I.B 23,800 1,170 30 1.6 Ex. I.9 I.B 55,700 2,750 82 2.5 Ex. I.10 I.B61,000 3,010 74 1.9 Ex. I.11 I.B 52,700 2,600 64 1.5 Ex. I.12 I.B 57,1002,820 82 2.6 Ex. I.13 I.C 68,200 2,980 78 2.6 C. Ex. C.C 31,800 1,830 952.7 I.1 at A

With reference to Tables 2 and 3, the inventive catalysts show muchhigher dimer selectivities than the control catalyst (C.Cat. A). Theunsaturations present within the dimer species produced by Catalyst I.A,Catalyst I.B, and Catalyst I.C in comparison to the conventionalcatalyst C.Cat. A are also shown. The dimers produced by Catalyst I.A,Catalyst I.B, and Catalyst I.C contain less than about 0.5 mol %vinylenes, about 3 mol % trisubstituted vinylenes, and greater thanabout 96 mol % vinylidene. In contrast, the conventional catalystproduces a very high amount of vinylenes at about 8 mol % and arelatively minimal amount of vinylidene at about 49 mol %. The inventivecatalysts also show a much higher catalyst productivity than theconventional catalyst. The catalyst productivity almost doubles that ofthe conventional catalyst.

Overall, the metallocene catalysts described herein can selectivelydimerize alpha-olefins to a product having very high vinylidene contentand very low vinylene content. In terms of processing, the catalystproductivity is significantly higher than conventional catalysts.Moreover, the catalysts show a much higher conversion to PAO dimer andless unreacted alpha-olefin monomer relative to conventional catalysts.Further the novel metallocene catalysts show a much lower conversion toPAO trimer, PAO tetramer, and higher oligomers of alpha-olefin relativeto conventional catalysts.

VII. B Examples—Process for Producing PAO Trimers from PAO Dimers

Metallocene dimer samples were prepared by oligomerizing a C₁₀ LAO usingan example metallocene catalyst (Catalyst I.A or Catalyst I.B) or acomparative catalyst (C.Cat. A), followed by a distillation. Their yieldto the desired hybrid trimer product can be compared.

Example Procedure for the BF₃-Catalyzed Reaction Using a Batch Reactor

Sample Ex. II.1: Example dimer was produced using the followingprocedure: An about 97% pure 1-decene was fed through an adsorbentcolumn filled with alumina to a stainless steel Parr vessel where it wassparged with nitrogen for 1 hour to obtain a purified feed. A catalystsolution including purified toluene, TNOA, and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (hereinafter referred to as “Activator1”) was prepared per the following recipe based on 1 gram of CatalystI.A: Catalyst I.A (1 g), purified toluene (394 g), TNOA (1 g), Activator1 (1.6 g). 200 g of 1-decene was pre-charged into a 2 gallon stainlesssteel Parr reactor and heated to 85° C. Then, additional 1-decene wasfed at 1040 g/hr co-currently with catalyst solution, which was fed at0.19 mL/min. The reactor was filled over a period of 2 hours at whichpoint the feeds were stopped. The reactor was pressured up to 25 psiunder a nitrogen atmosphere and held for 3 hours at a constant 85° C.After 3 hours, the reactor effluent was discharged, quenched by additionof water, and the reactor effluent collected in a product can. 0.2%cellulose was slurried into the reactor effluent and vacuum filtered.Then, dimer was isolated by vacuum batch distillation. Using 1H NMR, theapproximate unsaturation distribution was 97 mol % vinylidene, 3 mol %trisubstituted vinylene, and ˜0 mol % disubstituted vinylene.

The Example Dimer produced from the above procedure was mixed with1-octene in a composition of about 50 mol % metallocene PAO dimer andabout 50 mol % 1-octene and degassed by pulling a light vacuum in a Parrreactor. The catalyst system used was butanol/butyl acetate in a molarratio of about 1:1, saturated with BF₃. About 496 grams of the degassedolefin mixture was added along with the catalyst component (fed at aratio of about 15 mmol/100 g olefin) and fed into a 2 L stainless steelParr reactor over the span of about 1 hour. The reactor temperature wasabout 21° C. and pressure held at about 140 kPa (about 20 psia) under aBF₃ atmosphere. After about 1 hour, the reaction continued to react forabout 4 hours before the reactor effluent was discharged into a vesselfilled with 10% caustic. The resultant sample was water washed and theoil phase analyzed by GC.

Sample C.Ex. II.1: For the comparative example, the same procedure asabove for Sample Ex. II. 1 was used except the metallocene PAO dimer isComparative Dimer made per the procedure described in C.Ex. I.1.

Example Procedure for the BF₃-Catalyzed Reaction Using a CSTR

Sample Ex. II.2: Example dimer was collected as a composite from theprocedures described in Ex. I.1 and Ex. I.11. The unsaturateddistribution of this composite was approximated at roughly 97 mol %vinylidene, 3 mol % trisubstituted vinylene, and ˜0 mol % disubstitutedvinylene.

A composite of the Example Dimer from the sections above was taken andmixed with 1-decene in a composition of about 50 mol % metallocene dimerand 50 mol % 1-decene and degassed by pulling a light vacuum in a Parrreactor. The catalyst system used was butanol/butyl acetate in a molarratio of about 1:1, saturated with BF₃. The olefin mixture was addedalong with the catalyst component (fed at a ratio of about 15 mmol/100 golefin) and into a series of two 2 L stainless steel Parr reactor. Thereactor temperature for both reactors was about 21 C and held underabout 140 kPa (about 20 psia) of BF₃ atmosphere. The residence time ofthe first reactor was about 1.6 hours and the residence time of thesecond reactor was about 0.8 hours. The product was collected in avessel filled with 10% o caustic, water washed, and a sample of the oilphase was taken by GC.

Sample C.Ex. II.2: For the comparative example, the same procedure asabove for Sample Ex. II.2 was used except the metallocene PAO dimer isComparative Dimer as described in C.Ex. I.1.

TABLE 4 Dimer, Trimer, Sample PAO Dimer wt % wt % Tetramer+, wt %Product Mixture from Second Oligomerization - Batch Reactor Ex. II.1Example Dimer 9.0 82.9 8.1 C. Ex. II.1 Comparative Dimer 25.9 63.7 10.4Product Mixture from Second Oligomerization - CSTR Ex. II.2 ExampleDimer 4.0 82.7 13.3 C. Ex. II.2 Comparative Dimer 8.6 75.7 15.7

Table 4 shows that use of the Example Dimer in the secondoligomerization process provides significant yield advantages for thedesired PAO trimer product. The yield advantage over the ComparativeDimer in the second oligomerization is likely due to the quality of thedimer entering the second oligomerization process because thedisubstituted and trisubstituted vinylenes do not react in the secondoligomerization process. For example, the desired trimer product isformed at a very high yield of about 83 wt % from the Example Dimer,which has a much higher percentage of vinylidene (about 97 mol %) withlittle to no disubstituted vinylene (about 0 mol %) and very low amountsof trisubstituted vinylene (about 3 mol %). This is an improvement overthe conventional dimer for the second oligomerization process by about20 wt %. In addition, the conversion is much better for the exampledimer. For example, there is much less dimer in the example productmixture (less than about 9 wt %) relative to the comparative productmixture (about 26 wt %). With respect to the CSTR conditions, use of theexample dimer generates significantly higher yields of the desired PAOtrimer product, even when using identical reactor conditions in a singlecontinuous run. As shown in Table 4, there is an improvement in yield ofmore than about 7 wt %.

The “trimer region” (25 to 27.5 minutes) of the GC spectra from Ex. II.2was assessed to identify different trimer isomers. Peak regions 1, 2,and 3 illustrate isomerized trimer species. Peak 4 (at about 27 minutes)is the “hybrid trimer” peak. An integration of the peak area shows thefollowing composition: Peak 1—2.3 wt %; Peak 2—3.5 wt %; Peak 3—9.5 wt%; Peak 4—84.6 wt %.

The “trimer region” (25 to 27.5 minutes) of the GC spectra from C.Ex.II.2 was assessed to identify different trimer isomers. Peak regions 1,2, and 3 illustrate isomerized trimer species. Peak 4 (at about 27minutes) is the “hybrid trimer” peak. An integration of the peak areashows the following composition: Peak 1—2.1 wt % %; Peak 2—5.9 wt %;Peak 3—11.4 wt %; Peak 4—80.6 wt %.

Within the trimer region, peak 4 is present at 84.6 wt % in Ex.II.2 and80.6 wt % in C.Ex.II.2. So in addition to Ex. II.2 creating a greaterquantity of trimer, of the types of trimer species being formed, Ex.II.2 provided a higher concentration of hybrid trimer species as aresult of the improved processing conditions, which can provide improvedproduct properties.

Moreover, the second oligomerization process according to the presentdisclosure uses significantly less catalyst than conventional processes.Conventional processes use about 30 mmol of catalyst per 100 g LAO. Thesecond oligomerization process described herein can be performed usingfrom about 0.5 mmol to about 15 mmol of catalyst per 100 g LAO, such asfrom about 5 to about 15 mmol of catalyst per 100 g LAO. Furthermore,the second oligomerization process according to the present disclosurecan be performed at temperatures below 32° C., whereas conventionalprocesses are performed at 32° C.

The second oligomerization process described herein shows that a loweramount of disubstituted vinylene in the PAO dimer of the intermediatePAO can be more important than a higher amount of vinylidene in the PAOdimer of the intermediate PAO. A higher quality dimer is a dimer havinga low amount of disubstituted vinylene and, optionally, a lower amountof trisubstituted vinylene. The data shows a large increase in the yieldof the trimer can be effected by making a higher quality dimer. Inaddition, the selectivity towards the trimer over the undesired tetramerand heavies can be tuned by making a higher quality PAO dimer feedstock.Reducing the amount of disubstituted vinylene in the PAO dimer feedstockmakes the feedstock more reactive for the second oligomerizationprocess.

Conventional methods of forming hybrid trimers involve reaction of a PAOdimer feedstock that contains a significant amount of disubstitutedvinylene. The disubstituted vinylene, however, is not highly reactivewhen added to a BF₃ catalyzed conventional reactor, and the reactionkinetics are very slow. In addition, the unreacted dimer in the streamgoing into the BF₃ catalyzed conventional reactor contaminates thestream produced from the BF₃ process and reduces the value of thatby-product.

The methods described herein can overcome the problems with conventionalmethods by, at least, reducing (or eliminating) the amount ofdisubstituted vinylene in the PAO dimer feedstock.

VII. C Examples—Apparatus for Producing PAOs

In this example, PAO trimer produced from the metallocene reactor andhybrid trimer produced from the hybrid reactor are both collectivelyincluded in the term Trimer. Similarly, tetramer+ produced from themetallocene reactor and tetramer+ produced from the hybrid reactor areboth collectively included in the term tetramer+.

Table 5 shows a comparison of the product distribution produced by aconventional apparatus and an example apparatus in conjunction with acomparative catalyst and an inventive catalyst. The conventionalapparatus can have the configuration in FIG. 1 and can utilize eitherthe conventional, non-dimer selective catalyst C.Cat. A or the inventivecatalyst.

The example apparatus can have the same configuration as shown in FIG. 2and can utilize either the conventional, non-dimer selective catalystC.Cat. A or the inventive catalyst.

Using the inventive catalyst increases the yield of trimer from 66 kTato 83 kTa when using the conventional apparatus. This is a result of thehigh dimer selectivity afforded with use of the inventive catalyst.

Using the inventive apparatus in conjunction with the comparativecatalyst decreases the trimer yield from 66 kTa to 46 kTa. However, withthe use of the inventive catalyst, the trimer yield can actuallyincrease from 66 kTa to 75 kTa using this inventive and simplifiedapparatus.

TABLE 5 Amounts (kTa) LAO LAO Monomer/Catalyst Apparatus Feed 1 Feed 2Component Purge Dimer Trimer Tetramer+ Conventional 91  9 1 4 66 30 (C.Cat. A) Example III.1 88 12 1 4 83 13 (Catalyst I.B) Example III.2 100 —1 3 46 50 (C.Cat. A) Example III.3 100 — 1 7 75 17 (with Catalyst I.B)Values are shown in kilotons per annum (kTa), and are approximatevalues.

Conventional. Metallocene PAO reactor effluent was generated with thesame procedure as C. Ex. I. The expected yields using the conventionalapparatus was estimated had the mPAO dimer been reacted in the secondoligomerization as described in C.Ex. II.2.

Example III.1. Metallocene PAO reactor effluent was generated by theprocedure described in Ex. I.12. The expected yields using theconventional apparatus were estimated had the mPAO dimer been reacted inthe second oligomerization as described in Ex 1.2.

Example III.2. Metallocene PAO reactor effluent was generated with thesame procedure as C. Ex. I. The expected yields using the inventiveapparatus after the second oligomerization step as described in C.ExII.2 were estimated.

Example III.3. Metallocene PAO reactor effluent was generated in thesame manner as described as Ex. I.12. The expected yields using theinventive apparatus were determined with use of the following procedure:

The metallocene PAO reactor effluent was mixed with additional 1-deceneat a ratio of about 90% metallocene PAO reactor effluent, about 10%additional 1-decene. This mixture was sent to a degas vessel held at alight vacuum. The catalyst system used was butanol/butyl acetate in amolar ratio of about 1:1, saturated with BF₃. The olefin mixture wasadded along with the catalyst component (fed at a ratio of about 15mmol/100 g olefin) and into a series of two 2 L stainless steel Parrreactor. The reactor temperature for both reactors was about 21° C. andheld under about 140 kPa (about 20 psia) of BF₃ atmosphere. Theresidence time of the first reactor was about 0.7 hours and theresidence time of the second reactor was about 1.6 hours. The productwas collected in a vessel, quenched with caustic, water washed, and asample of the oil phase was taken by GC.

Table 6 shows the product distribution from the second oligomerizationstep.

TABLE 6 Second Oligomerization Effluent Example III.3 (wt %) Monomer &other lights 1 Dimer 7 Trimer 75 Tetramer+ & other heavies 17

The novel metallocene catalyst enables the production of a desirablemetallocene reactor product distribution having very low amounts oftrimers, tetramers, and higher oligomers. The novel metallocene dimeralso enables the production of a desirable PAO dimer composition havingvery low amounts of vinylenes. Because the product distribution of themetallocene reactor product has such low amounts of undesired products,the metallocene reactor product can be fed directly to the secondoligomerization reactor and without the use of a separation stage. Thenovel design allows the reduction of costs and the simplification ofoperation, while significantly improving the desired product yield.

In another variant, an amount of trimer can be blended with thetetramer+ as a stream in order to reduce the viscosity of the bottomproduct. In one example, the bottom stream will have 20% trimer in itscomposition in order to reduce the viscosity of the bottoms productstream to around a kinematic viscosity at 100° C. of 6 cSt. This can bebeneficial to create a high-valued co-product. The resulting products tobe produced would be as follows:

TABLE 7 Amounts (kTa) LAO LAO Monomer/Catalyst 20% trimer and ApparatusFeed 1 Feed 2 Component Purge Dimer Trimer 80% Tetramer+ Conventional 91 9 1 4 59 36 (C. Cat A) Conventional 88 12 1 4 79 17 (Catalyst I.B)Example III. 1 100 — 1 3 33 63 (C.Cat. A) Example III.2 100 — 1 7 71 21(with Catalyst I.B) Values are shown in kilotons per annum (kTa), andare approximate values.

As shown in Table 7, the novel catalyst still shows improved yields ofthe preferred total trimer product even when a portion of it is used tolower the viscosity of the bottoms stream in order to maximize itsvalue.

VII. D Examples—Functionalization of LAO Dimers and Trimers

Example 5 Alkylated Naphthalene from C20 mPAO dimer:

Overview:

A chemical product usable as a lubricant basestock was prepared byalkylating naphthalene with C20=umPAO (dimer of C10=LAO produced usingone of the inventive metallocene catalysts described in the presentdisclosure) with an acid catalyst.

Procedure:

A Parr reactor was charged with naphthalene (1.51 mol), a USY-H zeolitecatalyst (2.0 wt. %), and an inert hydrocarbon solvent (2.0 wt. %). Themixture was heated to 200° C. with stirring. C20=umPAO olefin (1.35 mol)was added to the reactor over a period of 60 minutes. The reactortemperature was increased to 210° C. for 90 minutes. Heating wasdiscontinued and the reactor contents filtered through Celite to removecatalyst. The filtrate was subjected to vacuum distillation to removeunreacted naphthalene and unreacted C20=umPAO olefin. The distillationpot bottoms contained a mixture of monoalkylated and dialkylatednaphthalene. This mixture was collected as the lubricant basestockproduct.

The properties of the Alkylated Naphthalene derived from the C20 mPAOdimer are shown below in Table 8:

TABLE 8 Property Units Method Value Wt. % total alkylate after 90minutes at 210° C. Wt % GC 90.36 Wt. % monoalkylate (of total alkylate)Wt % GC 90.5 Wt. % dialkylate (of total alkylate) Wt % GC 9.5 KinematicViscosity @ 100° C. cSt D445 6.95 Kinematic Viscosity @ 40° C. cSt D44554.1 Viscosity Index D2270 79 Pour Point ° C. D5950 −51 Noack Volatility% D5800 5.5 RPVOT Min D2272 164

Example 5. 1 Alkylated Naphthalene Testing in Driveline or ElectricVehicle Fluids

The Alkylated Naphthalene material isolated in Example 5 was then usedto formulate a driveline or electric vehicle fluid.

The table below (Table 9) shows the treat rate of the individualmaterials. Comparative examples are shown in Blends 2, 3, and 4, whichuse base stocks that are used widely in the industry today.

TABLE 9 Driveline/EV blend Blend# Component Blend 1 PAO 4 74.50% Yubase4 0.00% mPAO 150 0.50% Synnestic 5 Esterex A32 Inventive C20 AlkylatedNaphthalene 15.00% (Example 5) HiTec 3491LV 10.00% Property Base onMethod Properties Kinematic Viscosity @ cSt ASTM D445 5.328 100° C.Kinematic Viscosity @ cSt ASTM D445 25.76 40° C. Viscosity Index No-ASTM D2270 146 unit Pour Point ° C. ASTM D5950 Brookfield Viscosity@−40° C. cP ASTM D2983 5.010 RPVOT min D2272 783 Specific Gravity @ No-ASTM D4052 0.839 15.6° C. unit Driveline/EV blend Blend# Component Blend2 Blend 3 Blend 4 PAO 4 75.40% 72.80% Yubase 4 89.00% mPAO 150 4.60%2.20% 1.00% Synnestic 5 15.00% Esterex A32 10.00% Inventive C20Alkylated Naphthalene (Example 5) HiTec 3491LV 10.00% 10.00% 10.00%Property Base on Method Properties Kinematic Viscosity @ cSt ASTM D4455.662 5.634 5.493 100° C. Kinematic Viscosity @ cSt ASTM D445 26.0427.50 26.33 40° C. Viscosity Index No- ASTM D2270 167 150 152 unit PourPoint ° C. ASTM D5950 Brookfield Viscosity @−40° C. cP ASTM D2983 4,4708,060 12,380 RPVOT min D2272 1461 904 Specific Gravity @15.6° C. No-ASTM D4052 0.839 0.841 0.843 unit

The inventive C₂₀ alkylated naphthalene formulation has much higherviscosity index compared to the commercial example, while maintainingother critical properties such as low temperature performance and goodspecific gravity (high specific can contribute to higher energy/torquetransfer and improved heat transfer).

Example 5.2 Alkylated Naphthalene Testing in Industrial Oils

The Alkylated Naphthalene material isolated in Example 5 was then usedto formulate an industrial gear oil.

The table below (Table 10) shows the treat rate of the individualmaterials. A comparative example is shown in the first and second columnusing commercial materials available in the market today.

TABLE 10 Totals Product Blend 1 Blend 2 Blend 3 mPAO 150 65.00% 65.00%65.00% PAO 6 20.35% 20.35% 20.35% Inventive C20 12.00% AlkylatedNaphthalene (Example 5) Synnestie 5 12.00% Esterex A51 12.00% HiTec 3072.65% 2.65% 2.65% 100° C. ASTM D445 43.5 43.89 41.01 KinematicViscosity, cSt 40° C. Kinematic ASTM D445 338.3 350.4 331.3 Viscosity,cSt Viscosity index ASTM D2270 185.9 182.7 177.9 Brookfield ASTM D2983353,200 465,600 366,000 Viscosity @−40° C., cP Pour point, ° C. ASTMD5950 −51 −51 −51 RPVOT, min D2272 187 191 72

In the above example, the gear oil formulated with the inventive examplehad directionally poorer viscosity index and oxidative stability, withsimilar Brookfield viscosity to commercial formulations.

Example 5.3 Alkylated Naphthalene Testing in Compressor or HydraulicOils

The Alkylated Naphthalene material isolated in Example 5 was then usedto formulate a compressor or hydraulic oil.

The table below (Table 11) shows the treat rate of the individualmaterials. A comparative example is shown in the first column usingcommercial materials available in the market today.

TABLE 11 ISO 32 Properties Product Blend 1 Blend 2 SpectraSyn 4 44.13%SpectraSyn 6 20.00% SpectraSyn 8 24.13% Inventive C20 55.00% AlkylatedNaphthalene (Example 5) Synnestic 5 55.00% HiTec 521 0.87% 0.87% 100° C.Kinematic ASTM D445 5.464 5.311 Viscosity, cSt 40° C. Kinematic ASTMD445 30.66 30.71 Viscosity, cSt Viscosity index ASTM D2270 1.15 105 PourPoint, ° C. ASTM D97 −45 −63 Flash Point, ° C. ASTM D93 >200 >200 RPVOT,min ASTM D2272 462 360

In the above example, the compressor or hydraulic fluid formulated withthe inventive example had directionally poorer viscosity index andoxidative stability, but with an improved pour point.

Example 6 Alkylated Anisole from C20 mPAO Dimer

Overview:

A chemical product usable as a lubricant basestock was prepared byalkylating anisole with C20=umPAO (dimer of C10=LAO using one of theinventive metallocene catalysts described in the present disclosure)with an acid catalyst.

Procedure:

A reactor was charged with anisole (3.50 mol) and a USY-H zeolitecatalyst (2.0 wt %). The mixture was heated to 150° C. with stirring.C20=umPAO olefin (3.12 mol) was added to the reactor over a period of 60minutes. The reaction continued for an additional 90 minutes. Heatingwas discontinued and the reactor contents filtered through celite toremove catalyst. The filtrate was subjected to vacuum distillation toremove unreacted anisole and unreacted C20=umPAO olefin. Thedistillation pot bottoms contained primarily monoalkylated anisole withonly trace amounts of dialkylated anisole. This mixture was collected asthe lubricant basestock product. The properties of the Alkylated Anisolederived from the C20 mPAO dimer are shown below (Table 12).

TABLE 12 Test Units Method Value Wt. % total alkylate 90 Wt % GC 76.2minutes after olefin addition at 150° C. Wt. % monoalkylate (of total Wt% GC >99% alkylate) Wt. % dialkylate (of total Wt % GC  <1% alkylate)Kinematic Viscosity @ 100° C. cSt D445 4.6 Kinematic Viscosity @ 40° C.cSt D445 26.8 Viscosity Index D2270 72 Pour Point ° C. D5950 −63 NoackVolatility % D5800 13.0 RPVOT Min D2272 395

Example 6.1 Alkylated Anisole Testing in Driveline or Electric VehicleFluids

The Alkylated Anisole material isolated in Example 6 was then used toformulate a driveline or electric vehicle fluid.

The table below (Table 13) shows the treat rate of the individualmaterials. Comparative examples are shown in Blends 2, 3, and 4, whichuse base stocks that are used widely in the industry today.

TABLE 13 Driveline/EV blend Blend# Component Blend 1 Blend 2 PAO 472.80% 75.40% Yubase 4 0.00% 0.00% mPAO 150 2.20% 4.60% Synnestic 5Estercx A32 10.00% Inventive C20 15.00% Alkylated Anisole (Example 6)HiTec 3491LV 10.00% 10.00% Property Base on Method Property KinematiccSt ASTM D445 5.959 5.662 Viscosity @ 100° C. Kinematic cSt ASTM D44530.10 26.04 Viscosity @ 40° C. Viscosity Index No-unit ASTM D2270 148167 Pour Point ° C. ASTM D5950 −69 loaded Brookfield cP ASTM D2983 6,8604,470 Viscosity @−40° C. RPVOT min D2272 1073 1461 Specific GravityNo-unit ASTM D4052 0.841 0.839 @ 15.6° C. Driveline/EV blend Blend#Component Blend 3 Blend 4 PAO 4 72.80% Yubase 4 0.00% 89.00% mPAO 1502.20% 1.00% Synnestic 5 15.00% Esterex A32 Inventive C20 AlkylatedAnisole (Example 6) HiTec 3491LV 10.00% 10.00% Property Base on MethodProperty Kinematic cSt ASTM D445 5.634 5.493 Viscosity @ 100° C.Kinematic cSt ASTM D445 27.50 26.330 Viscosity @ 40° C. Viscosity IndexNo- ASTM D2270 150 152 unit Pour Point ° C. ASTM D5950 Brookfield cPASTM D2983 8,060 12,380 Viscosity @−40° C. RPVOT min D2272 904 SpecificGravity No- ASTM D4052 0.841 0.843 @ 15.6° C. unit

The formulation containing the inventive alkylated anisole had excellentlow temperature properties, and excellent oxidative stability (indicatedby RPVOT results). The inventive-containing formulation also has higherspecific gravity than Blend 2, and comparable specific gravity to Blend3 and 4. High specific gravity formulations can contribute to higherenergy/torque transfer and improved heat transfer.

Example 6.2 Alkylated Anisole Testing in Industrial Oils

The Alkylated Anisole material isolated in Example 6 was then used toformulate an industrial gear oil.

The table below (Table 14) shows the treat rate of the individualmaterials. A comparative example is shown in the first and second columnusing commercial materials available in the market today.

TABLE 14 Totals Product Blend 1 Blend 2 Blend 3 mPAO 150 65.00% 65.00%65.00% PAO 6 20.35% 20.35% 20.35% Inventive C20 12.00% Alkylated Anisole(Example 6) Synnestic 5 12.00% Esterex A51 12.00% HiTec 307 2.65% 2.65%2.65% 100° C. Kinematic ASTM D445 43.5 43.89 43.9 Viscosity, cSt 40° C.Kinematic ASTM D445 338.3 350.4 353.3 Viscosity, cSt Viscosity indexASTM D2270 185.9 182.7 181.6 Brookfield Viscosity ASTM D2983 353,200465,600 360,000 @ −40° C., cP Pour point, ° C. ASTM D3950 −51 −51 −54RPVOT, min D2272 187 191 91

In the above example, the gear oil formulated with the inventive examplehad directionally poorer viscosity index and oxidative stability, withsimilar Brookfield viscosity to commercial formulations.

Example 6.3 Alkylated Anisole Testing in Compressor or Hydraulic Oils

The Alkylated Anisole material isolated in Example 6 was then used toformulate a compressor or hydraulic oil.

The table below (Table 15) shows the treat rate of the individualmaterials. A comparative example is shown in the first column usingcommercial materials available in the market today.

TABLE 15 ISO 32 Properties Product Blend 1 Blend 2 SpectraSyn 4SpectraSyn 6 20.00% 15.00% SpectraSyn 8 24.13% 29.13% C20-Alkyl Anisole55.00% Synnestic 5 55.00% HiTce 521 0.87% 0.87% 100° C. Kinematic ASTMD445 5.464 5.501 Viscosity, cSt 40° C. Kinematic ASTM D445 30.66 31.33Viscosity, cSt Viscosity index ASTM D2270 115 112 Pour Point, ° C. ASTMD97 −45 −66 Flash Point, ° C. ASTM D93 >200 >200 RRVOT, min ASTM D2272462 371

In the above example, the compressor or hydraulic fluid formulated withthe inventive example had directionally poorer viscosity index andoxidative stability, but with an improved pour point.

VII. E Examples—First Oligomerization

Synthesis of catalysts I.C and 21-22 was described in earlier section.

Synthesis of the following catalysts and characterization thereof, aswell as polymerizations using the catalysts can be found in U.S. Ser.No. 16/270,085, filed Feb. 7, 2019.

TABLE 16 Catalyst 0.08 μmol (0.4 mmol/l in toluene) (MC), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (Activator 1)activator (0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Conditions ActivityMn* % Mn* Temp (g/ Olefins Distribution (%) Yield (g/ Conv. Vinylidene(avg) Ex. # MC (° C.) s · mol) Di Vi Tri Vd (g) mol) %** (avg) (g/mol) 1a 1A 60 1370 0.7 3.6 2.6 93.1 0.394 1166 26.6 93.5 1153 b 60 1420 0.53.4 2.3 93.8 0.409 1140 27.6 2 a 1A 85 2320 0.3 3.3 2.6 93.7 0.669 55545.1 93.8 538 b 85 2050 0.4 3.1 2.7 93.8 0.589 520 39.7 3 a 1A 110 28100.2 1.0 2.9 96.0 0.809 371 54.6 95.9 372 b 110 2810 0.2 1.2 2.8 95.80.809 372 54.6 4 a B 60 721 0.3 4.5 3.8 91.4 0.208 1282 14.0 91.4 1285 b60 745 0.0 4.6 4.1 91.3 0.215 1287 14.5 5 a B 85 1460 0.3 5.1 4.3 90.30.421 632 28.4 89.8 636 b 85 1470 0.4 5.5 4.8 89.3 0.424 640 28.6 6 a B110 2170 0.2 3.3 5.3 91.2 0.625 413 42.2 91.2 415 b 110 2250 0.2 3.4 5.491.1 0.649 417 43.8 7 a 1A/B 60 1090 0.5 3.8 2.8 92.9 0.314 1203 21.292.6 1191 b (1:1) 60 1100 0.7 3.8 3.2 92.3 0.318 1178 21.5 8 a 1A/B 851940 0.7 4.3 4.3 90.6 0.558 572 37.7 91.4 581 b (1:1) 85 1900 0.4 4.23.3 92.1 0.547 589 36.9 9 a 1A/B 110 2280 0.3 3.1 4.0 92.6 0.658 40244.4 93.1 405 b (1:1) 110 2680 0.2 2.5 3.8 93.5 0.772 408 52.1 10 a C 60555 — 2.7 2.5 94.7 0.160 967 10.8 94.5 982 b 60 651 — 3.1 2.7 94.2 0.188996 12.7 11 a C 85 1440 — 3.9 3.4 92.8 0.416 535 28.1 93.5 541 b 85 1220— 3.1 2.7 94.2 0.351 546 23.7 12 a C 110 2980 — 1.6 3.0 95.5 0.860 36158.0 95.5 361 b 110 3290 — 1.4 3.2 95.4 0.947 361 63.9 13 a D 60 38200.9 23.0 3.4 72.6 1.10 3004 74.2 72.9 3039 b 60 3830 0.9 22.9 3.0 73.21.10 3074 74.2 14 a D 85 4340 1.2 12.0 4.3 82.5 1.25 987 84.3 83.3 1012b 85 4360 0.5 12.2 3.2 84.1 1.26 1036 85.0 15 a D 110 4130 0.5 5.9 3.490.2 1.19 578 80.3 90.0 577 b 110 4140 0.5 6.5 3.2 89.8 1.19 576 80.3 16a E 60 4240 3.7 6.4 3.8 86.1 1.22 4550 82.3 85.3 4445 b 60 4270 3.9 6.15.5 84.5 1.23 4339 83.0 17 a E 85 4540 2.3 2.1 6.8 88.8 1.31 1285 88.488.8 1288 b 85 4600 2.3 1.9 7.1 88.7 1.32 1291 89.1 18 a E 110 4050 1.44.1 6.1 88.4 1.17 729 78.9 87.7 723 b 110 4050 1.8 4.3 7.0 86.9 1.17 71778.9 19 a F^(C) 60 4370 3.3 — 7.3 89.4 1.26 1048 85.0 89.2 1044 b 604350 3.4 — 7.5 89.0 1.25 1040 84.3 20 a F^(C) 85 4380 4.1 — 11.6 84.31.26 551 85.0 84.3 551 b 85 4450 4.1 — 11.6 84.2 1.28 550 86.4 21 aF^(C) 110 4230 5.7 — 16.5 77.8 1.22 402 82.3 77.8 409 b 110 4240 5.6 —16.8 77.7 1.22 415 82.3 22 a G^(C) 60 1600 0.8 6.0 9.8 83.3 0.462 351931.2 83.4 3612 b 60 1540 0.9 6.0 9.8 83.4 0.443 3704 29.9 23 a G^(C) 852120 1.2 8.3 12.9 77.5 0.610 1311 41.2 78.9 1321 b 85 1990 0.5 7.6 11.680.2 0.572 1330 38.6 24 a G^(C) 110 1740 1.0 8.7 15.8 74.6 0.502 70233.9 74.9 702 b 110 1520 0.9 8.6 15.4 75.1 0.438 701 29.6 25 a H^(C) 602480 — 33.4 19.4 47.2 0.713 6554 48.1 49.2 6863 b 60 2590 — 33.4 15.451.2 0.745 7172 50.3 26 a H^(C) 85 3050 0.7 37.5 17.2 44.6 0.880 216759.4 44.6 2212 b 85 2600 0.9 37.4 17.2 44.5 0.748 2256 50.5 27 a H^(C)110 1660 0.7 30.8 17.6 50.9 0.478 953 32.3 51.3 892 b 110 2280 0.9 28.618.9 51.7 0.658 830 44.4 28 a J 60 1730 1.2 1.6 12.3 84.9 0.499 238633.7 84.3 2372 b 60 1740 1.4 1.9 12.9 83.7 0.502 2358 33.9 29 a J 852730 1.4 2.1 16.8 79.7 0.787 867 53.1 79.9 878 b 85 2870 1.3 2.0 16.680.0 0.826 888 55.7 30 a J 110 2910 1.4 1.6 20.8 76.2 0.838 509 56.576.3 511 b 110 2890 1.3 1.5 20.9 76.3 0.832 513 56.1 31 a K^(c) 60 412012.3  0.0 16.0 71.6 1.19 12368 80.3 67.6 12286 b 60 3970 15.9  0.0 20.663.5 1.14 12203 76.9 32 a K^(c) 85 4570 5.5 4.3 18.2 72.1 1.32 4740 89.172.0 4902 b 85 4610 5.5 4.4 18.2 71.9 1.33 5064 89.7 33 a K^(c) 110 38304.3 11.3 17.3 67.1 1.10 3020 74.2 66.5 3007 b 110 3710 4.4 11.4 18.465.8 1.07 2993 72.2 34 a L 60 485 9.6 — 12.5 77.9 0.140 1930 9.4 78.21959 b 60 486 9.8 — 11.8 78.4 0.140 1988 9.4 35 a L 85 815 8.1 0.4 12.179.4 0.235 864 15.9 79.1 863 b 85 887 8.3 0.6 12.4 78.7 0.256 861 17.336 a L 110 1330 8.9 0.4 14.2 76.5 0.383 534 25.8 75.8 525 b 110 1310 9.40.5 15.0 75.1 0.377 515 25.4 *Mn estimated by ¹H NMR; **Conv. %calculated from isolated yield and it is the minimum conversion due tovolatility of the dimer product; ^(c)Comparative catalysts andpolymerization examples.

TABLE 17 Catalyst 0.08 μmol (0.4 mmol/l in toluene) (MC), with 0.08 μmolN,N-Dimethylanilinium tetrakisperfluoronaphthylborate activator (0.4mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l in isohexane), 2mL 1-Decene, isohexane solvent 1 h. Conditions Activity OlefinsDistribution (%) Mn* Ex. # MC Temp (° C.) (g/s · mol) Di Vi Tri Vd Yield(g) (g/mol) Conv. %** 37 a 1A 60 696 1.2 7.3 8.8 82.7 0.200 1885 13.5 b60 663 1.1 7.2 8.6 83.2 0.191 2009 12.9 38 a 1A 85 1350 0.9 7.6 7.6 83.80.388 772 26.2 b 85 1280 0.6 7.4 7.4 84.6 0.369 796 24.9 39 a 1A 1102050 0.4 5.5 6.6 87.5 0.590 456 39.8 b 110 2340 0.4 5.2 6.7 87.7 0.674460 45.5 40 a D 60 2600 1.0 34.7 8.7 55.6 0.750 4353 50.6 b 60 2500 1.733.2 10.3 54.8 0.719 4353 48.5 41 a D 85 3280 1.0 31.9 6.4 60.7 0.9461405 63.8 b 85 3480 0.9 30.8 7.4 60.9 1.00 1349 67.5 42 a D 110 3850 1.019.3 5.8 73.9 1.11 657 74.9 b 110 3690 0.7 21.8 6.6 71.0 1.06 669 71.5*Mn estimated by ¹ H NMR. **Conv. % calculated from isolated yield andit is the minimum conversion due to volatility of the dimer product.

TABLE 18 Catalyst 0.08 μmol (0.4 mmol/l in toluene) (MC), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (Activator 1)activator (0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Isolated % Mn* TYield % % % % Mn* Vinylidene (avg) Conv. Ex. # (° C.) MC (g) VinyleneTri-sub Vinyl Vinylidene g/mol (avg) (g/mol) %** 43A 60 1A 0.3942 0.72.6 3.6 93.1 1166 93.5 1153 26.6 43B 60 1A 0.4087 0.5 2.3 3.4 93.8 114027.6 44A 85 1A 0.6694 0.3 2.6 3.3 93.7 555 93.8 537 45.2 44B 85 1A0.5894 0.4 2.7 3.1 93.8 520 39.8 45A 110 1A 0.8086 0.2 2.9 1.0 95.9 37195.9 372 54.6 45B 110 1A 0.8092 0.2 2.8 1.2 95.8 372 54.6 46A 60 20.1097 0.4 1.1 0.8 97.8 504 97.9 519 7.4 46B 60 2 0.1064 0.4 1.0 0.797.9 533 7.2 47A 85 2 0.194 0.1 0.8 0.1 99.0 324 99.0 325 13.1 47B 85 20.1762 0.1 0.8 0.2 98.9 327 11.9 48A 110 2 0.3025 0.2 1.3 0.2 98.3 30398.5 303 20.4 48B 110 2 0.2614 0.1 1.1 0.1 98.7 303 17.6 49A 60 Cat.0.1548 0.3 0.7 0.9 98.1 622 97.7 620 10.4 I.A 49B 60 Cat. 0.1594 0.4 1.11.3 97.2 618 10.8 I.A 50A 85 Cat. 0.4458 0.8 2.1 1.2 95.9 367 97.0 37330.1 I.A 50B 85 Cat. 0.4442 0.2 0.9 0.7 98.2 379 30.0 I.A 51A 110 Cat.0.8584 0.1 1.3 0.2 98.4 320 98.1 317 57.9 I.A 51B 110 Cat. 0.8568 0.31.6 0.4 97.7 315 57.8 I.A 52A 60 4 0.1827 0.3 3.1 4.7 91.9 1313 91.91298 12.3 52B 60 4 0.1844 0.3 3.2 4.6 91.9 1284 12.4 53A 85 4 0.7312 0.13.5 6.7 89.8 722 89.5 710 49.3 53B 85 4 0.5846 0.2 4.0 6.6 89.2 699 39.454A 110 4 0.8993 0.3 4.7 5.8 89.2 426 89.8 430 60.7 54B 110 4 0.9406 0.24.0 5.4 90.4 435 63.5 *Mn estimated by ¹ H NMR; **Conv % calculated fromisolated yield and it is the minimum conversion due to volatility of thedimer product.

TABLE 19 Catalyst 0.08 μmol (0.4 mmol/l in toluene) (MC), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (Activator 1)activator (0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Isolated % Mn* TYield % % % % Mn* Vinylidene (avg) Conv. Ex. # (° C.) MC (g) VinyleneTri-sub Vinyl Vinylidene g/mol (avg) (g/mol) %** 55A 60 5 1.2132 1.5 5.72.4 90.4 2552 90.4 2592 81.9 55B 60 5 1.1997 1.5 5.7 2.4 90.4 2632 81.056A 85 5 1.2801 1.2 8.9 1.2 88.8 914 88.7 917 86.4 56B 85 5 1.2557 1.29.1 1.1 88.6 921 84.7 57A 110 5 1.1828 1.1 11.4  1.0 86.5 534 86.1 53679.8 57B 110 5 1.2055 1.2 12.1  1.0 85.7 538 81.3 58A 60 6 0.0278 0.60.6 0.3 98.5 552 98.1 551 1.9 58B 60 6 0.0285 0.6 1.1 0.6 97.6 549 1.959A 85 6 0.1436 0.4 1.0 0.4 98.2 356 98.1 353 9.7 59B 85 6 0.1477 0.41.1 0.4 98.1 351 10.0 60A 110 6 0.3657 0.5 1.5 0.3 97.8 314 98.1 31424.7 60B 110 6 0.3488 0.2 1.1 0.2 98.4 315 23.5 61A 60 7 0.1337 0.6 4.07.2 88.2 1919 87.2 1913 9.0 61B 60 7 0.1306 0.6 5.2 7.8 86.3 1907 8.862A 85 7 0.1532 0.5 5.4 9.3 84.8 872 85.4 874 10.3 62B 85 7 0.1626 0.54.6 8.9 86.0 876 11.0 63A 110 7 0.1944 0.4 4.9 8.8 85.9 507 86.2 52013.1 63B 110 7 0.2602 0.3 4.7 8.5 86.4 532 17.6 64A 60 Cat. I.B 0.12460.5 1.2 1.0 97.3 583 96.6 588 8.4 64B 60 Cat. I.B 0.1245 0.5 1.9 1.896.0 593 8.4 65A 85 Cat. I.B 0.4319 0.2 1.2 0.8 97.8 369 97.8 368 29.165B 85 Cat. I.B 0.4452 0.2 1.2 0.7 97.9 367 30.0 66A 110 Cat. I.B 0.89730.0 1.1 0.2 98.6 317 98.4 317 60.5 66B 110 Cat. I.B 0.9322 0.1 1.4 0.398.2 317 62.9 67A 60 9 0.0323 0.0 3.3 1.3 95.4 507 95.3 513 2.2 67B 60 90.0326 0.0 3.3 1.6 95.1 518 2.2 68A 85 9 0.1665 0.0 3.2 0.7 96.1 33096.4 327 11.2 68B 85 9 0.1832 0.0 3.0 0.4 96.6 325 12.4 69A 110 9 0.18240.0 2.3 0.3 97.4 309 97.3 307 12.3 69B 110 9 0.226 0.0 2.5 0.4 97.1 30615.2 70A 60 10 0.0695 0.5 1.3 1.3 96.8 794 97.5 794 4.7 70B 60 10 0.06220.4 1.2 0.1 98.2 794 4.2 71A 85 10 0.0821 0.3 1.3 2.0 96.4 490 96.7 4895.5 71B 85 10 0.0913 0.3 1.1 1.7 97.0 488 6.2 72A 110 10 0.1419 0.1 1.21.2 97.4 362 97.3 361 9.6 72B 110 10 0.1801 0.2 1.3 1.3 97.2 360 12.273A 60 11 0.0917 0.3 0.8 1.0 97.9 636 97.3 630 6.2 73B 60 11 0.092 0.41.4 1.5 96.7 625 6.2 74A 85 11 0.2414 0.1 0.9 1.1 98.0 406 98.0 399 16.374B 85 11 0.2651 0.1 0.9 1.0 98.0 393 17.9 75A 110 11 0.6764 0.0 1.2 0.598.3 317 98.3 317 45.6 75B 110 11 0.6827 0.0 1.1 0.5 98.4 317 46.1 76A60 12 0.039 — — — — — — — 2.6 76B 60 12 0.0351 — — — — — 2.4 77A 85 120.1596 0.3 1.5 0.2 98.0 344 97.8 345 10.8 77B 85 12 0.1621 0.3 1.7 0.497.6 346 10.9 78A 110 12 0.2002 0.8 2.7 0.0 96.4 311 97.2 313 13.5 78B110 12 0.2236 0.3 1.7 0.0 98.0 315 15.1 79A 60 13 0.5464 3.4 5.3 2.389.0 1191 91.0 1246 36.9 79B 60 13 0.5493 2.6 3.4 1.0 93.0 1301 37.1 80A85 13 0.8176 1.6 4.5 0.6 93.4 550 93.3 553 55.2 80B 85 13 0.8451 1.6 4.60.6 93.2 557 57.0 81A 110 13 0.9876 1.3 6.8 0.1 91.8 382 91.9 383 66.681B 110 13 0.9961 1.2 6.7 0.1 91.9 385 67.2 82A 60 14 0.0467 — — — — — —— 3.2 82B 60 14 0.0462 — — — — — 3.1 83A 85 14 0.1268 4.0 3.7 1.8 90.5854 90.4 847 8.6 83B 85 14 0.1369 3.9 3.8 1.9 90.3 839 9.2 84A 110 140.0899 2.0 5.1 2.6 90.4 593 90.6 585 6.1 84B 110 14 0.0912 1.6 5.0 2.490.9 577 6.2 85A 60 15 0.0207 — — — — — — — 1.4 85B 60 15 0.0209 — — — —— 1.4 86A 85 15 0.0974 0.3 1.4 0.9 97.4 365 97.6 361 6.6 86B 85 150.1094 0.4 1.3 0.6 97.7 358 7.4 87A 110 15 0.2949 1.2 2.7 0.7 96.0 29897.2 305 19.9 87B 110 15 0.3415 0.3 1.2 0.1 98.4 312 23.0 88A 60 160.1052 0.5 4.2 6.8 88.6 1780 89.3 1770 7.1 88B 60 16 0.1152 0.4 3.3 6.290.1 1760 7.8 89A 85 16 0.1241 0.6 4.9 8.9 85.6 857 83.9 815 8.4 89B 8516 0.1415 1.4 7.7 8.8 82.2 773 9.5 90A 110 16 0.1986 0.3 5.5 10.4  83.8661 85.3 586 13.4 90B 110 16 0.2248 0.4 4.6 8.2 86.8 511 15.2 91A 60 170.0195 — — — — — — — 1.3 91B 60 17 0.0189 — — — — — 1.3 92A 85 17 0.0735— — — — — — — 5.0 92B 85 17 0.0929 — — — — — 6.3 93A 110 17 0.2384 0.21.3 0.4 98.1 314 97.1 310 16.1 93B 110 17 0.2354 0.9 2.4 0.6 96.1 30515.9 *Mn estimated by ¹H NMR; **Conv % calculated from isolated yieldand it is the minimum conversion due to volatility of the dimer product.“—” indicates insufficient material for analysis or data not available.

TABLE 20 Catalyst 0.04 μmol (0.8 mmol/l in toluene) (MC), with 0.04 μmolN,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate as activator(0.8 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-decene, isohexane solvent, 1 h. Isolated % Mn* TYield % % % % Mn* Vinylidene (avg) Ex. # (° C.) MC (g) Vinylene Tri-subVinyl Vinylidene g/mol (avg) (g/mol) Conv. %** 94A 85 18 0.0594 0.5% 6.35.1 88.2 521 87.6 533 4.0 94B 85 18 0.0539 0.6% 7.2 5.2 87.0 546 3.6 95A85 19 0.1231 0.7% 4.3 3.8 91.3 492 91.5 496 8.3 95B 85 19 0.1287 0.6%4.2 3.5 91.7 501 8.7 *Mn estimated by ¹ H NMR. **Conv % calculated fromisolated yield and it is the minimum conversion due to volatility of thedimer product.

TABLE 21 Catalyst 0.08 μmol (0.4 mmol/l in toluene) (MC), with 0.08 μmolN,N-Dimethylanilinium Tetrakisperfluorophenylborate (Activator 1)activator (0.4 mmol/l in toluene), about 0.6 μmol of TNOA (0.01 mol/l inisohexane), 2 mL 1-Decene, isohexane solvent, 1 h. Polymerizationprocedure and characterization method were analogous to that describedin USSN 16/270,085. Isolated % Mn* T Yield % % % % Mn* Vinylidene (avg)Conv. Ex. # (° C.) MC (g) Vinylene Tri-sub Vinyl Vinylidene g/mol (avg)(g/mol) %**  96A 60 4 0.2356 0.3 1.1 0.6 98.0 459 98.4 455 15.9  96B 604 0.2440 0.2 0.8 0.4 98.6 457 16.5  97A 85 4 0.7848 0.1 1.0 0.3 98.6 32098.5 320 53.0  97B 85 4 0.8154 0.2 1.1 0.2 98.4 319 55.0  98A 110 40.9963 0.1 1.2 0.2 98.6 303 98.3 302 67.2  98B 110 4 1.0326 0.2 1.2 0.298.5 303 69.7  96C 60 4 0.2439 0.3 0.9 0.5 98.4 453 16.5  96D 60 40.2524 0.2 0.8 0.5 98.5 452 17.0  97C 85 4 0.7783 0.2 1.1 0.3 98.5 32152.5  97D 85 4 0.8072 0.2 1.1 0.2 98.6 319 54.5  98C 110 4 1.0651 0.11.1 0.1 98.7 303 71.9  98D 110 4 1.0187 0.5 1.7 0.3 97.5 297 68.7  99A60 Cat. I.C 0.1845 0.2 1.2 0.3 98.3 418 98.3 419 12.4  99B 60 Cat. I.C0.1800 0.2 1.3 0.3 98.1 414 12.1 100A 85 Cat. I.C 0.7116 0.2 1.7 0.298.0 317 98.1 318 48.0 100B 85 Cat. I.C 0.7393 0.1 1.5 0.2 98.2 318 49.9101A 110 Cat. I.C 0.9879 0.2 1.7 0.1 98.1 300 98.2 301 66.7 101B 110Cat. I.C 1.0074 0.1 1.6 0.1 98.1 301 68.0  99C 60 Cat. I.C 0.1728 0.21.4 0.3 98.1 420 11.7  99D 60 Cat. I.C 0.1675 0.1 1.1 0.3 98.5 424 11.3100C 85 Cat. I.C 0.7074 0.1 1.6 0.2 98.1 318 47.7 100D 85 Cat. I.C0.7492 0.1 1.5 0.2 98.2 318 50.6 101C 110 Cat. I.C 0.9942 0.1 1.5 0.198.3 302 67.1 101D 110 Cat. I.C 0.9777 0.0 1.5 0.1 98.3 302 66.0 102A 6021 0.3051 0.1 0.5 0.2 99.3 362 99.1 360 20.6 102B 60 21 0.3027 0.2 0.60.2 99.0 359 20.4 103A 85 21 0.8871 0.1 0.7 0.1 99.1 308 99.1 308 59.9103B 85 21 0.9261 0.1 0.7 0.1 99.1 308 62.5 104A 110 21 1.0198 0.1 0.80.1 99.0 299 98.9 298 68.8 104B 110 21 1.0143 0.1 0.8 0.1 98.9 298 68.4102C 60 21 0.2995 0.1 0.6 0.1 99.1 361 20.2 102D 60 21 0.3067 0.2 0.60.1 99.1 359 20.7 103C 85 21 0.8404 0.1 0.7 0.1 99.1 308 56.7 103D 85 210.9171 0.1 0.7 0.1 99.1 307 61.9 104C 110 21 1.0324 0.2 0.9 0.1 98.8 29769.7 104D 110 21 1.0181 0.1 0.8 0.1 99.0 298 68.7 105A 60 22 0.1025 0.20.7 0.2 98.8 395 98.9 397 6.9 105B 60 22 0.0976 0.2 0.7 0.2 99.0 400 6.6106A 85 22 0.6733 0.1 1.0 0.1 98.7 309 98.6 310 45.4 106B 85 22 0.67770.1 1.1 0.1 98.7 310 45.7 107A 110 22 0.9701 0.1 1.3 0.1 98.5 297 98.3296 65.5 107B 110 22 0.9234 0.1 1.1 0.1 98.7 297 62.3 105C 60 22 0.10590.1 0.7 0.2 99.0 396 7.1 105D 60 22 0.0988 0.2 0.8 0.4 98.7 399 6.7 106C85 22 0.6181 0.1 1.0 0.1 98.8 311 41.7 106D 85 22 0.6426 0.3 1.4 0.398.1 309 43.4 107C 110 22 0.9484 0.2 1.2 0.1 98.5 297 64.0 107D 110 220.8789 0.4 1.6 0.3 97.7 294 59.3 *Mn in this table estimated by ¹ H NMRusing methods described in U.S.S.N. 16/270,085: **Conv % calculated fromisolated yield and it is the minimum conversion due to volatility of thedimer product.

Note that runs in Ex. 52A-54B appear to be outliers as re-runs withmetallocene 4 in Ex. 96A-98D all appear to give lower Mn and highervinylidene % at similar conditions.

VII. F. End Use Examples Example 1

Isolating C₁₀ dimer+C₁₀ LAO (C₃₀) using inventive two-step process.

The catalyst batch includes Hf based metallocene catalysts shown in theexamples and those mentioned in U.S. Ser. No. 16/270,085, a Lewis acidactivator, scavenger and a solvent.

A feed comprising C₁₀ alpha-olefin was contacted with the catalystsystem described above in a polymerization reactor using the proceduredescribed in Ex. II.2.

The C₃₀ material was hydrogenated to a Bromine number less than 1 in astainless steel Parr reactor at 232° C. and 2413 kPa (350 psi) ofhydrogen for 2 hours using 0.5 wt % Nickel catalyst in a slurry reactor.The C30 material was vacuum filtered to remove residual catalyst.

The C₃₀ material was then analyzed and properties are shown below (Table22A):

TABLE 22A Based on Property Method UNIT Property Kinematic ASTM D445 cSt3.516 Viscosity @ 100° C. Kinematic ASTM D445 cSt 14.21 Viscosity @ 40°C. Viscosity Index ASTM D2270 No-unit 130 Pour Point, ° C. ASTM D5950 °C. −78 Brookfield @−40° C. ASTM D2983 cP 1,488 Noack Volatility, ASTMD5800, wt % 12.31 evaporation loss % Procedure B RPVOT ASTM D2272minutes 102 CCS Apparent ASTM D5293 cP 362 Viscosity @−25° C. CCSApparent ASTM D5293 cP 571 Viscosity @−30° C. CCS Apparent ASTM D5293 cP903 Viscosity @−35° C. HTHS Apparent ASTM D5481 cP 1.377 Viscosity @150° C. MRV Apparent SWRI/ASTM cP 1,300 Viscosity @−40° C. D4684 Flashpoint (COC) - SWRI/ASTM ° C. 223 open cup D92

The results above indicate that the C₃₀ material isolated above hasexcellent low viscosity with exceptional volatility and low-temperatureproperties. Additionally the oxidative stability (RPVOT) is improvedabove conventional low vis PAOs produced strictly from Lewis-Acidprocessing steps.

Example I.1 C₃₀ Testing in Engine Oils

The C₃₀ material isolated in the inventive two-step process described inExample I was then used to formulate an engine oil.

TABLE 22B Engine Oil Blend 1 Blend 2 Blend# Component (KV100° C.) 0W-200W-20 Inventive C30 PAO 13.00% 29.20% (Example 1) Gr II 4 cSt 67.00%0.00% Gr II 5 cSt 0.00% 50.80% AN 5 5.00% 5.00% Infineum SV203 5.00%5.00% Infineum P6003 ™ 10.00% 10.00% Total 100.00% 100.00% Property UNITBased on Method Kinematic cSt ASTM D445 8.923 9.473 Viscosity @ 100° C.Kinematic cSt ASTM D445 53.89 52.59 Viscosity @ 40° C. Viscosity IndexNo-unit ASTM D2270 145 166 Pour Point ° C. ASTM D5950 −30 −33 CCSApparent cP ASTM D5293 2,042 2,044 Viscosity @−25° C. CCS Apparent cPASTM D5293 3,513 3,466 Viscosity @−30° C. CCS Apparent cP ASTM D52936,493 6,193 Viscosity @−35° C. MRV Apparent cP SWRI/ASTM D4684 44,30028,500 Viscosity @−40° C. HTHS Apparent cP ASTM D5481 2.947 2.952Viscosity @ 150° C. Noack Volatility, wt % ASTM D5800, Procedure B 12.0211.18 evaporation loss

The results above indicate that the C₃₀ inventive material provides theengine oil with excellent low temperature properties, even when blendedwith high concentrations of low-quality Gr II base stocks. Thevolatility of the blend was also very low, thanks to the low volatilityof the C₃₀ material.

Example I.2 C₃₀ Testing in Driveline or Electric Vehicle Fluids

The C₃₀ material isolated in the inventive two-step process described inExample 1 was then used to formulate a driveline or electric vehiclefluid.

The table below (Table 22C) shows the treat rate of the individualmaterials. A comparative example is shown in the first column usingconventional PAO material, which are derived from standard BF₃-catalystprocesses.

TABLE 22C Driveline/EV fluids Component/Blend# Blend 1 Blend 2 InventiveC30 PAO 88.00% (Example 1) PAO 2 15.20% PAO 4 72.80% HiTEC 3419D 12.00%12.00% Property Base on Method Data Kinematic Viscosity cSt ASTM D4454.106 4.156 @ 100° C. Kinematic Viscosity cSt ASTM D445 18.27 17.91 @40° C. Viscosity Index No-unit ASTM D2270 128 139 Pour Point ° C. ASTMD5950 −75 −75 Brookfield Viscosity cP ASTM D2983 2,550 2,340 @ −40° C.Oxidation Stability, min ASTM D2272 686 658 RPVOT Noack Volatility, %run at 200 C. 7.118 1.69 evaporation loss (200 C.) MTM Traction FIG. 7(80° C.)

The viscosity index of the inventive example was much better thanstandard PAO blend. The volatility was also much lower, since theformulation does not require use of high volatility molecules such asPAO 2. This is an example of how uniquely tailored molecules haveadvantages over commercial molecules. While the comparative blend hassimilar viscosity, the inventive example achieves higher viscosity indexand drastically lower volatility, which are both highly desirableproperties for driveline and electric vehicle fluids.

Example I.3 C₃₀ Testing in Industrial Oils

The C₃₀ material isolated in the inventive two-step process described inExample 1 was then used to formulate an industrial gear oil. Thebenefits exhibited in this example can also be applied to automotivegear oils which have similar formulations approaches.

The table below (Table 23) shows the treat rate of the individualmaterials. A comparative example is shown in the first column using PAO4 material, which is a PAO produced from a BF₃ catalyzed process and iswidely used in the industry.

TABLE 23 ISO 320 Product Blend 1 Blend 2 mPAO 150 66.35% 67.61%SpectraSyn 4 19.00% Inventive C30 PAO 17.74% (Example 1) Esterex A5112.00% 12.00% HiTec 307  2.65%  2.65% 100° C. Kinematic ASTM D445 42.3642.76 Viscosity, cSt 40° C. Kinematic ASTM D445 320.6 320.3 Viscosity,cSt Viscosity index ASTM D2270 188 190 Brookfield Viscosity ASTM D2983300,600 268,200 @ −40° C., cP Pour point, ° C. ASTM D5950 −54 −54 RPVOT(mm) D2272 53 55 MTM (80° C.) Standard method FIG. 8

The inventive material provides, inter alia, two advantages:

-   -   The inventive lower viscosity material allows for wider bi-modal        blend of the two primary base stocks (i.e. the viscosity        difference is wider between the two PAO base stocks used in each        blend), which provides improved viscosity index, and lower        traction coefficient compared to the commercial example    -   The low-temperature performance of the inventive fluid is better        than commercial materials

Example I.4 C₃₀ Testing in Compressor or Hydraulic Oils

The C₃₀ material isolated in the inventive two-step process described inExample 1 was then used to formulate a compressor or hydraulic fluid.

The table below (Table 24) shows the treat rate of the individualmaterials. A comparative example is shown in the first column using PAO4 and PAO 8 material, which is a PAO produced from a BF₃ catalyzedprocess and is widely used in the industry.

TABLE 24 ISO 32 Product Property Product Blend 1 Blend 2 SpectraSyn 431.50% Inventive C30 23.76% PAO (Example 1) SpectraSyn 8 47.63% 55.37%Synnestic 5 20.00% 20.00% HiTec 521  0.87%  0.87% 100° C. Kinematic ASTMD445 5.669 5.702 Viscosity, cSt 40° C. Kinematic ASTM D445 30.14 30.00Viscosity, cSt Viscosity index ASTM D2270 131 134 Pour Point, ° C. ASTMD97 −54 −51 Flash Point, ° C. ASTM D93 >200 >200 RPVOT, min ASTM D2272326 321 MTM (80° C.) Standard method FIG. 9

When comparing the two blends, the inventive material's lower viscositymaterial allows for wider bi-modal blend of the two primary base stocks(i.e. the viscosity difference is wider between the two PAO base stocksused in each blend), which provides improved viscosity index, and lowertraction coefficient compared to the commercial example.

Example 2: Isolating C₆ Dimer+C₆ LAO (C₁₈) Using Inventive Two-StepProcess

The catalyst batch includes Hf based metallocene catalysts shown in theexamples and those mentioned in U.S. Ser. No. 16/270,085, a Lewis acidactivator, scavenger and a solvent.

A feed comprising of C₆ alpha-olefin was contacted with the catalystsystem described above in a polymerization reactor under the followingpolymerization conditions.

A 1-hexene stream was fed through an adsorbent column filled withalumina adsorbent to a stainless steel Parr vessel where it was spargedwith nitrogen for 1 hour to obtain a purified feed. The catalyst wasCatalyst I.A. A catalyst solution including purified toluene, TNOA, andN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafterreferred to as “Activator 1”) was prepared per the following recipebased on 1 gram of Catalyst I.A: Catalyst I.A (1 g), purified toluene(394 g), TNOA (0.67 g), Activator 1 (1.6 g). The olefin feedstream wasadded at a rate of about 1,040 grams per hour to a 1 gallon stainlesssteel Parr reactor held at about 140° C. for oligomerization. The1-hexene and catalyst solution were fed into the reactor at a ratio ofabout 55,700 grams of LAO per gram of catalyst. The residence time inthe reactor was about 2.9 hours. The reactor was run at liquid fullconditions, with no addition of any gas. When the system reachedsteady-state, a reactor effluent was collected and quenched by additionof deionized water. Cellulose was slurried into the reactor effluent at0.2 wt % and the material taken through a vacuum filtration. Theconversion and oligomer distribution was determined by GC. The dimer wasthen isolated by vacuum distillation.

The resulting distribution of oligomers is shown below (Table 25):

TABLE 25 Distribution from metallocene reaction C₆ Monomer & otherlights (wt %) 20.3 C₁₂ Dimer (wt %) 67.1 C₁₈ Trimer (wt %) 8.3 C₂₄+Heavies (wt %) 4.3

The dimer portion was then isolated through distillation. The dimerportion was then fed to an acid catalyst reaction (BF₃), along with a1:1 molar ratio of C₆ alpha olefin under the following reactionconditions:

i) The dimer from above was added to 1-hexene in a composition of about50 mol % metallocene PAO and 50 mol % 1-hexene and degassed by pulling alight vacuum in a Parr reactor. The catalyst system used wasbutanol/butyl acetate in a molar ratio of about 1:1, saturated with BF₃.Catalyst was added co-currently with the catalyst system components at aratio of 15 mmol catalyst/100 g LAO and fed into a 2 L stainless steelParr reactor over the span of about 2 hours. The reactor temperature wasabout 21° C. and pressure held at about 140 kPa (about 20 psia) under aBF₃ atmosphere. After the 2 hour addition period, the reaction continuedto react for about 4 hour before the reactor effluent was dischargedinto a vessel filled with 10% caustic. The resultant sample was waterwashed and the oil phase analyzed by GC.

The resulting distribution of oligomers is shown below (Table 26).

TABLE 26 Distribution from BF₃ reaction C₆ Monomer & other lights (wt %)~0 C₁₂ Dimer (wt %) 2.2 C₁₈ Trimer (wt %) 42.2 C₂₄+ Heavies (wt %) 55.6

An overall yield of C₁₈ material can be calculated based on a massbalance, and is shown below (Table 27):

TABLE 27 Yield of C₁₈ material Inventive example using HD catalyst 28.3

The C₁₈ material was hydrogenated to a Bromine number less than 1 in astainless steel Parr reactor at 232° C. and 2413 kPa (350 psi) ofhydrogen for 2 hours using 0.5 wt % Nickel catalyst in a slurry reactor.The C₁₈ material was vacuum filtered to remove residual catalyst.

The C₁₈ material was then analyzed and properties are shown below (Table28):

TABLE 28 Based Property on Method UNIT Result Kinematic Viscosity @ 100°C. ASTM D445 cSt 1.341 Kinematic Viscosity @ 40° C. ASTM D445 cSt 3.688Viscosity Index ASTM D2270 No-unit 78 Pour Point, ° C. ASTM D5950 ° C.−96 CCS Apparent Viscosity @ −35° C. ASTM D5293 cP 306 MTM traction @ 80C. Standard MTM FIG. 10

The inventive example provides a very unique balance having very-lowviscosity with excellent cold-temperature properties. The PAO would beideal for use in cooling, driveline, and electric vehicle fluids.

In FIG. 9, the MTM traction is compared against a commercial 4 cSt PAOproduced from BF₃ catalyst processes widely used in the industry. Theinventive example provides exceptionally low traction.

Example 3: Isolating C₁₂ Dimer+C8 LAO (C32) Using Inventive Two-StepProcess

The catalyst batch includes Hf based metallocene catalysts shown in theexamples and those mentioned in U.S. Ser. No. 16/270,085, a Lewis acidactivator, scavenger and a solvent.

A feed comprising C₁₂ alpha-olefin was contacted with the catalystsystem described above in a polymerization reactor under the followingpolymerization conditions.

A 1-dodecene stream was fed through an adsorbent column filled withalumina adsorbent to a stainless steel Parr vessel where it was spargedwith nitrogen for 1 hour to obtain a purified feed. The catalyst wasCatalyst I.A. A catalyst solution including purified toluene, TNOA, andN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafterreferred to as “Activator 1”) was prepared per the following recipebased on 1 gram of Catalyst I.A: Catalyst I.A (1 g), purified toluene(394 g), TNOA (0.67 g), Activator 1 (1.6 g). The olefin feedstream wasadded at a rate of about 1,040 grams per hour to a 1 gallon stainlesssteel Parr reactor held at about 140° C. for oligomerization. The1-dodecene and catalyst solution were fed into the reactor at a ratio ofabout 59,600 grams of LAO per gram of catalyst. The residence time inthe reactor was about 2.9 hours. The reactor was run at liquid fullconditions, with no addition of any gas. When the system reachedsteady-state, a reactor effluent was collected and quenched by additionof deionized water. Cellulose was slurried into the reactor effluent at0.2 wt % and the material taken through a vacuum filtration. Theconversion and oligomer distribution was determined by GC. The dimer wasthen isolated by vacuum distillation.

The resulting distribution of oligomers is shown below (Table 29):

TABLE 29 Distribution from metallocene reaction C₁₂ Monomer & otherlights (wt %) 19.3 C₂₄ Dimer (wt %) 73.8 C₃₆ Trimer (wt %) 5.5 C₄₈₊Heavies (wt %) 1.4

The dimer portion was then isolated through distillation. The dimerportion was then fed to an acid catalyst reaction (BF₃), along with a1:1 molar ratio of C₈ alpha olefin under the following reactionconditions:

The dimer from above was added to 1-octene in a composition of about 50mol % metallocene dimer and 50% 1-octene and degassed by pulling a lightvacuum in a Parr reactor. The catalyst system used was butanol/butylacetate in a molar ratio of about 1:1, saturated with BF₃. Catalyst wasadded co-currently with the catalyst system components at a ratio of 15mmol catalyst/100 g LAO and fed into a 2 L stainless steel Parr reactorover the span of about 2 hours. The reactor temperature was about 21° C.and pressure held at about 140 kPa (about 20 psia) under a BF₃atmosphere. After the 2 hour addition period, the reaction continued toreact for about 4 hours before the reactor effluent was discharged intoa vessel filled with 10% caustic. The resultant sample was water washedand the oil phase analyzed by GC.

The resulting distribution of oligomers is shown below (Table 30).

TABLE 30 Distribution from BF₃ reaction C₈ & other lights (wt %) 2.7C₁₆-C₂₄ (wt %) 13.8 C₃₂ (desired) (wt %) 71.5 C₃₆₊ Heavies (wt %) 12.0

An overall yield of C₃₂ material (desired product) can be calculatedbased on a mass balance, and is shown below (Table 31):

TABLE 31 Yield of C₃₂ material (desired product) Inventive example usingHD catalyst 52.8

The C₃₂ material was hydrogenated to a Bromine number less than 1 in astainless steel Parr reactor at 232° C. and 2413 kPa (350 psi) ofhydrogen for 2 hours using 0.5 wt % Nickel catalyst in a slurry reactor.The C₃₂ material was vacuum filtered to remove residual catalyst.

The C₃₂ material was then analyzed and properties are shown below (Table32) and FIG. 10:

TABLE 32 Based Property on Method UNIT Property Kinematic Viscosity @100° C. ASTM D445 cSt 4.004 Kinematic Viscosity @ 40° C. ASTM D445 cSt16.9 Viscosity Index ASTM D2270 No-unit 138 Pour Point, ° C. ASTM D5950° C. −57 Noack Volatility, evaporation ASTM D5800, wt % 7.89 loss %Procedure B Brookfield @ −40° C. ASTM D2983 cP 2034 CCS ApparentViscosity @ ASTM D5293 cP 1180 −35° C.

The inventive C₃₂ PAO has a similar viscosity to commercial 4 cSt PAOsproduced from BF₃ processes widely used in the industry. The inventiveexample has an exceptionally low volatility and excellent lowtemperature properties.

In FIG. 11, the MTM traction is compared against a commercial 4 cSt PAOproduced from BF₃ catalyst processes widely used in the industry. Theinventive example provides exceptionally low traction compared to thecommercial material.

Example 4: Isolating C₁₂ Dimer+C₆ LAO (C₃₀) Using Inventive Two-StepProcess

The catalyst batch includes Hf based metallocene catalysts shown in theexamples and those mentioned in U.S. Ser. No. 16/270,085, a Lewis acidactivator, scavenger and a solvent.

A feed comprising of C₁₂ alpha-olefin was contacted with the catalystsystem described above in a polymerization reactor under the followingpolymerization conditions.

A 1-dodecene stream was fed through an adsorbent column filled withalumina adsorbent to a stainless steel Parr vessel where it was spargedwith nitrogen for 1 hour to obtain a purified feed. The catalyst wasCatalyst I.A. A catalyst solution including purified toluene, TNOA, andN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafterreferred to as “Activator 1”) was prepared per the following recipebased on 1 gram of Catalyst I.A: Catalyst I.A (1 g), purified toluene(394 g), TNOA (0.67 g), Activator 1 (1.6 g). The olefin feedstream wasadded at a rate of about 1,040 grams per hour to a 1 gallon stainlesssteel Parr reactor held at about 140° C. for oligomerization. The1-dodecene and catalyst solution were fed into the reactor at a ratio ofabout 59,600 grams of LAO per gram of catalyst. The residence time inthe reactor was about 2.9 hours. The reactor was run at liquid fullconditions, with no addition of any gas. When the system reachedsteady-state, a reactor effluent was collected and quenched by additionof deionized water. Cellulose was slurried into the reactor effluent at0.2 wt % and the material taken through a vacuum filtration. Theconversion and oligomer distribution was determined by GC. The dimer wasthen isolated by vacuum distillation.

The resulting distribution of oligomers is shown below (Table 33):

TABLE 33 Distribution from metallocene reaction C₁₂ Monomer & otherlights (wt %) 19.3 C₂₄ Dimer (wt %) 73.8 C₃₆ Trimer (wt %) 5.5 C₄₈₊Heavies (wt %) 1.4

The dimer portion was then isolated through distillation. The dimerportion was then fed to an acid catalyst reaction (BF₃), along with a1:1 molar ratio of C₆ alpha olefin under the following reactionconditions:

a) The dimer from above was added to 1-hexene in a composition of about50 mol % metallocene dimer and 50 mol % 1-hexene and degassed by pullinga light vacuum in a Parr reactor. The catalyst system used wasbutanol/butyl acetate in a molar ratio of about 1:1, saturated with BF₃.Catalyst was added co-currently with the catalyst system components at aratio of 15 mmol catalyst/i 100 g LAO and fed into a 2 L stainless steelParr reactor over the span of about 2 hours. The reactor temperature wasabout 21° C. and pressure held at about 140 kPa (about 20 psia) under aBF₃ atmosphere. After the 2 hour addition period, the reaction continuedto react for about 4 hours before the reactor effluent was dischargedinto a vessel filled with 10% caustic. The resultant sample was waterwashed and the oil phase analyzed by GC.

The resulting distribution of oligomers is shown below (Table 34).

TABLE 34 Distribution from BF₃ reaction C₆ & other lights (wt %) <0.1C₁₂-C₂₄ (wt %) 17.4 C₃₀ (desired) (wt %) 65.7 C₃₆₊ Heavies (wt %) 17.0

An overall yield of C₃₀ material (desired product) can be calculatedbased on a mass balance, and is shown below (Table 35):

TABLE 35 Yield of C₃₀ material (desired product) Inventive example usingHD catalyst 48.9

The C₃₀ material was hydrogenated to a Bromine number less than 1 in astainless steel Parr reactor at 232° C. and 2413 kPa (350 psi) ofhydrogen for 2 hours using 0.5 wt % Nickel Oxide catalyst in a slurryreactor. The C₃₀ material was vacuum filtered to remove residualcatalyst.

The C₃₀ material was then analyzed and properties are shown below (Table36) and FIG. 11:

TABLE 36 Property Based on Method UNIT Property Kinematic Viscosity @ASTM D445 cSt 3.74 100° C. Kinematic Viscosity @ ASTM D445 cSt 15.58 40°C. Viscosity Index ASTM D2270 No-unit 138 Pour Point, ° C. ASTM D5950 °C. −54 Noack Volatility, ASTM D5800, wt % 11.75 evaporation loss %Procedure B Brookfield @ −40° C. ASTM D2983 cP 1902 CCS ApparentViscosity ASTM D5293 cP 1071 @ −35° C.

The results indicate that the C₃₀ material isolated above has excellentlow viscosity with exceptional volatility and low-temperatureproperties.

In FIG. 12, the MTM traction is compared against a commercial 4 cSt PAOproduced from BF₃ catalyst processes widely used in the industry. Theinventive example provides exceptionally low traction compared to thecommercial material.

The results from this experiment are remarkably similar to the resultsshown in Example 1, where a C₃₀ material was obtained using the two-stepprocess with 1-decene. When comparing Example 1 and Example 5, it isevident that the two-step process with dimer-selective catalyst allowssignificant feed flexibility not achievable with current technology. Forexample, Example 5 provides a product remarkably similar to Example 1(similar properties and same carbon number), but with a completelydifferent set of LAO feeds. This type of feed-flexibility is highlydesirable to base stock manufacturers in order to ensure reliable feedsupply and to improve economics with lower cost feeds. The inventivecatalyst of the present disclosure provides commercial application ofthat feed flexibility.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the present disclosure have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe present disclosure. Accordingly, it is not intended that the presentdisclosure be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including.” Likewise whenever acomposition, an element or a group of elements is preceded with thetransitional phrase “comprising,” it is understood that we alsocontemplate the same composition or group of elements with transitionalphrases “consisting essentially of,” “consisting of,” “selected from thegroup of consisting of,” or “is” preceding the recitation of thecomposition, element, or elements and vice versa.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, within a range includes everypoint or individual value between its end points even though notexplicitly recited. Thus, every point or individual value may serve asits own lower or upper limit combined with any other point or individualvalue or any other lower or upper limit, to recite a range notexplicitly recited.

What is claimed is:
 1. A process to produce a poly alpha-olefin (PAO), comprising: introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the metallocene compound is represented by the formula:

wherein: each of R¹, R², and R³ is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl group, wherein a first one of R¹, R², and R³ is not hydrogen and at least one of R¹, R², and R³ is hydrogen; each of R⁴, R⁵, R⁶, and R⁷ is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C₁-C₃₀ hydrocarbyl group, or one or more pair of R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷, taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings fused to the indenyl ring; each of R⁸, R⁹, R¹⁰, R¹¹ and R¹² is independently a substituted or unsubstituted linear, branched, or cyclic C₁-C₃₀ hydrocarbyl, silylcarbyl, or germanyl group; M is a group 3, 4 or 5 transition metal; each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C₁-C₂₀ substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and m is an integer equal to 1, 2, or
 3. 2. The process of claim 1, wherein the metallocene compound is represented by the formula:

wherein: each of R¹, R², and R³ is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl or silylcarbyl group; each of R⁴ and R⁷ is independently a substituted or unsubstituted linear, branched linear, or cyclic C₁-C₃₀ hydrocarbyl or silylcarbyl group; each of R⁸, R⁹, R¹⁰, R¹¹ and R¹² is independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl, silylcarbyl, or germanyl group, or optionally at least three of R⁸, R⁹, R¹⁰ and R¹² are not hydrogen; each of R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl or silylcarbyl group; M is a group 3, 4 or 5 transition metal; each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C₁-C₂₀ substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and m is an integer equal to 1, 2, or
 3. 3. The process of claim 1, wherein the first alpha-olefin is one or more C₆-C₃₂ alpha-olefin.
 4. The process of claim 1, wherein the second alpha-olefin is one or more C₆-C₃₂ alpha-olefin.
 5. The process of claim 1, wherein the acid catalyst is a Lewis acid.
 6. The process of claim 1, wherein the second reactor conditions comprise an acid catalyst loading of from about 5 mmolCat/100 gLAO to about 15 mmolCat/100 gLAO.
 7. The process of claim 1, wherein the second reactor conditions comprise a temperature of from about 10° C. to about 40° C.
 8. The process of claim 1, wherein the acid catalyst is BF₃.
 9. The process of claim 1, wherein the amount of PAO trimer in the second reactor effluent is 75 wt % or more, based on a total weight of PAO dimer, PAO trimer, and higher oligomers, where the higher oligomers are oligomers that have degree of polymerization of 4 or more, of alpha-olefin in the second reactor effluent.
 10. The process of claim 1, wherein the second reactor effluent comprises, 75 wt % or more of PAO trimer, 9 wt % or less of PAO dimer, and 16 wt % or less of higher oligomers of alpha-olefin, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent.
 11. The process of claim 1, wherein the amount of PAO trimer in the second reactor effluent is greater than 80 wt %, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent.
 12. The process of claim 1, wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: up to 4 mol % of trisubstituted vinylene, up to 4 mol % of disubstituted vinylene, or up to 4 mol % of trisubstituted vinylene and disubstituted vinylene.
 13. A process to produce a poly alpha-olefin (PAO), comprising: introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the PAO dimer in the first reactor effluent comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: 98 mol % or more vinylidene, and up to 2 mol % of trisubstituted vinylene, and/or disubstituted vinylene.
 14. The process of claim 1, wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: 98 mol % or more vinylidene, and up to 1 mol % trisubstituted vinylene, up to 1 mol % disubstituted vinylene, or up to 1 mol % trisubstituted vinylene and disubstituted vinylene.
 15. The process of claim 1, wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: 98 mol % or more vinylidene, and up to 0.5 mol % trisubstituted vinylene, up to 0.5 mol % disubstituted vinylene, or up to 0.5 mol % trisubstituted vinylene and disubstituted vinylene.
 16. The process of claim 1, wherein the activator comprises one or more of: N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorophenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate alumoxane, modified alumoxane, and aluminum alkyl.
 17. The process claim 1, wherein the second catalyst composition further comprises an alcohol and an alkyl acetate.
 18. The process of claim 1, wherein the metallocene compound is selected from the group consisting of:

and a combination thereof.
 19. The process of claim 1, wherein the second reactor conditions include a second reactor temperature of less than 60° C. and an acid catalyst composition loading of less than 30 mmol per 100 g of second alpha-olefin.
 20. The process of claim 1, further comprising functionalizing the PAO trimer with a reactant to form a functionalized PAO product.
 21. The process of claim 20, further comprising hydrogenating the PAO dimer, PAO trimer, or functionalized PAO product to form a hydrogenated PAO product.
 22. The process of claim 21, wherein the hydrogenated PAO product has a kinematic viscosity at 100° C. of from 3.4 to 4.0 cSt and a Noack volatility (y) that does not exceed the value defined by the following equation, where x is the kinematic viscosity at 100° C.: y=−21.0x ²+148.7x−248.9.
 23. The process of claim 1 wherein the process that produces the first reactor effluent has a conversion of at least 60%, based upon the weight of the monomer entering the reactor and the PAO produced and a selectivity for dimer of at least 85 wt %, based upon the PAO produced.
 24. The process of claim 23, wherein one of R¹, R², and R³ is a substituted or unsubstituted linear, branched, or cyclic C₁-C₆ hydrocarbyl group, and two of R¹, R², and R³ are each a hydrogen.
 25. The process of claim 24, wherein each X is independently a halogen or a substituted or unsubstituted linear, branched, or cyclic C₁-C₆ hydrocarbyl group; M comprises Zr or Hf and m is
 2. 26. The process of claim 23, wherein M is Zr, m is 2 and each X is independently a methyl, an ethyl, a propyl, a butyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide.
 27. The process of claim 23 wherein the a polymerization reactor is a continuous stirred tank reactor or a continuous tubular reactor, the alpha-olefin is introduced to the reactor at a flow rate of at least 100,000 g/hr, the polymerization residence time is from 2 to 5 hours, and the polymerization temperature is 120° C. or more.
 28. The process of claim 27 where the vinylidene content of the PAO produced is 96% or more based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO product, the Mn of the PAO product is 350 g/mol or less, the conversion is at least 80% based upon the weight of the monomer entering the reactor and the PAO produced, the PAO dimer selectivity is at least 60%, based upon the weight of the PAO produced, and the productivity of the continuous process is at least 60,000 g/hour with a catalyst loading of 0.1 gram catalyst per gram of monomer or less.
 29. A process to produce a poly alpha-olefin (PAO), comprising: introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the metallocene compound is represented by the formula:

wherein: each of R¹, R², and R³ is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl or silylcarbyl group; each of R⁴ and R⁷ is independently a substituted or unsubstituted linear, branched, or cyclic C₁-C₃₀ hydrocarbyl or silylcarbyl group; each of R⁸, R⁹, R¹⁰, R¹¹ and R¹² is independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl, silylcarbyl, or germanyl group, or optionally at least three of R⁸, R⁹, R¹⁰, R¹¹ and R¹² are not hydrogen; each of R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C₁-C₂₀ hydrocarbyl or silylcarbyl group; M is a group 3, 4 or 5 transition metal; each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C₁-C₂₀ substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and m is an integer equal to 1, 2, or
 3. 30. The process of claim 29, wherein: the first alpha-olefin is one or more C₆-C₃₂ alpha-olefin, the second alpha-olefin is one or more C₆-C₃₂ alpha-olefin, the acid catalyst is BF₃, and the second reactor effluent comprises, 75 wt % or more of PAO trimer, 9 wt % or less of PAO dimer, and 16 wt % or less of higher oligomers of alpha-olefin, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent. 